Nonaqueous electrolytes and nonaqueous-electrolyte secondary batteries employing the same

ABSTRACT

A subject is to provide a nonaqueous electrolyte excellent in cycle performances such as capacity retention after cycling, output after cycling, discharge capacity after cycling, and cycle discharge capacity ratio, output characteristics, high-temperature storability, low-temperature discharge characteristics, heavy-current discharge characteristics, high-temperature storability, safety, high capacity, high output, high-current-density cycle performances, compatibility of these performances, etc. Another subject is to provide a nonaqueous-electrolyte secondary battery employing the nonaqueous electrolyte. The subjects have been accomplished with a nonaqueous electrolyte which contains a monofluorophosphate and/or a difluorophosphate and further contains a compound having a specific chemical structure or specific properties.

TECHNICAL FIELD

The present invention relates to nonaqueous electrolytes for secondarybatteries and to nonaqueous-electrolyte secondary batteries employingthe electrolytes. More particularly, the invention relates to nonaqueouselectrolytes containing a specific ingredient, and tononaqueous-electrolyte secondary batteries employing the electrolytes.

BACKGROUND ART

With the recent trend toward size reduction in electronic appliances,secondary batteries are increasingly required to have a higher capacity,etc. Attention is hence focused on lithium secondary batteries, whichhave a higher energy density than nickel-cadmium batteries andnickel-hydrogen batteries.

The electrolytes used in lithium secondary batteries are nonaqueouselectrolytes prepared by dissolving an electrolyte such as LiPF₆, LiBF₄,LiClO₄, LiCF₃SO₃, LiAsF₆, LiN(CF₃SO₂)₂, or LiCF₃(CF₂)₃SO₃ in anonaqueous solvent such as acyclic carbonate, e.g., ethylene carbonateor propylene carbonate, a chain carbonate, e.g., dimethyl carbonate,diethyl carbonate, or ethyl methyl carbonate, a cyclic ester, e.g.,γ-butyrolactone or γ-valerolactone, a chain ester, e.g., methyl acetateor methyl propionate, or the like.

<Nonaqueous Electrolytes 1 and 1-1, Nonaqueous-Electrolyte SecondaryBatteries 1 and 1-1>:

First, such nonaqueous-electrolyte secondary batteries have advantagesof having a high energy density and being less apt to sufferself-discharge. In recent years, the secondary batteries are henceextensively used as power sources for mobile appliances for public use,such as portable telephones, notebook personal computers, and PDAs. Theelectrolytes for nonaqueous-electrolyte secondary batteries areconstituted of a lithium salt as a supporting electrolyte and anonaqueous organic solvent. The nonaqueous organic solvent is requiredto have a high permittivity for dissociating the lithium salt, to showhigh ionic conductivity in a wide temperature range, and to be stable inthe batteries. It is difficult to meet these requirements with a singlesolvent. Because of this, use is generally made of a combination of ahigh-boiling solvent represented by propylene carbonate, ethylenecarbonate, or the like and a low-boiling solvent such as dimethylcarbonate or diethyl carbonate.

On the other hand, many reports have been made on the addition ofvarious additives to electrolytes in order to improve initial capacity,rate characteristics, cycle performances, high-temperature storability,continuous-charge characteristics, self-discharge characteristics,overcharge-preventive properties, etc. For example, addition of alithium fluorophosphate compound has been reported as a technique forinhibiting self-discharge at high temperatures (see patent document 1).

<Nonaqueous Electrolyte 2 and Nonaqueous-Electrolyte Secondary Battery2>:

Secondly, various investigations have been made on nonaqueous solventsand electrolytes in order to improve the battery characteristicsincluding output characteristics, cycle performances, and storability ofthose lithium secondary batteries. For example, patent document 2describes a technique in which a battery having excellentlow-temperature output characteristics is produced by using anelectrolyte containing a tetrafluoroboric acid salt in a certain amountrelative to the overall area of the active-material layer formed on thepositive-electrode current collector.

This technique has, in some degree, the effect of improving outputcharacteristics without reducing high-temperature cycle performances.However, the degree of output improvement attainable with this techniqueis limited, and the technique failed to attain an even higher output.

<Nonaqueous Electrolyte 3 and Nonaqueous-Electrolyte Secondary Battery3>:

Thirdly, various investigations have been made on nonaqueous solventsand electrolytes in order to improve the battery characteristicsincluding load characteristics, cycle performances, storability, andlow-temperature characteristics of those lithium secondary batteries.For example, patent document 3 includes a statement to the effect thatwhen an electrolyte containing a vinylethylene carbonate compound isused, the decomposition of this electrolyte is minimized and a batteryexcellent in storability and cycle performances can be fabricated.Patent document 4 includes a statement to the effect that when anelectrolyte containing propanesultone is used, recovery capacity afterstorage can be increased.

The incorporation of such compounds can produce, in some degree, theeffect of improving storability and cycle performances. However, thosetechniques have had a problem that a coating film having high resistanceis formed on the negative-electrode side and this, in particular,reduces discharge load characteristics.

<Nonaqueous Electrolyte 4 and Nonaqueous-Electrolyte Secondary Battery4>:

Fourthly, various investigations have been made on nonaqueous solventsand electrolytes in order to improve the battery characteristicsincluding load characteristics, cycle performances, storability, andlow-temperature characteristics of those lithium secondary batteries.For example, patent document 3 includes a statement to the effect thatwhen an electrolyte containing a vinylethylene carbonate compound isused, the decomposition of this electrolyte is minimized and a batteryexcellent in storability and cycle performances can be fabricated.Patent document 4 includes a statement to the effect that when anelectrolyte containing propanesultone is used, recovery capacity afterstorage can be increased.

The incorporation of such compounds produces, in some degree, the effectof improving storability and cycle performances. However, thosetechniques have had a problem that a coating film having high resistanceis formed on the negative-electrode side and this, in particular,reduces discharge load characteristics.

On the other hand, it has been reported in patent document 5 that theaddition of a compound represented by the formula (1) given in patentdocument 5 improves both cycle performances and current characteristics.It has also been reported in patent document 6 that the addition of aspecific compound improves low-temperature discharge characteristics.

However, battery characteristics such as load characteristics, cycleperformances, storability, and low-temperature characteristics are stillinsufficient, and there has been room for improvement.

<Nonaqueous Electrolyte 5 and Nonaqueous-Electrolyte Secondary Battery5>:

Fifthly, nonaqueous-electrolyte batteries including lithium secondarybatteries are coming to be practically used in extensive applicationsranging from power sources for applications for public use, such as,e.g., portable telephones and notebook personal computers, to on-vehiclepower sources for driving motor vehicles or the like. However, recentnonaqueous-electrolyte batteries are increasingly required to havehigher performances, and there is a desire for improvements in bothbattery characteristics and battery safety.

Electrolytes for use in nonaqueous-electrolyte batteries are usuallyconstituted mainly of an electrolyte and a nonaqueous solvent. As maincomponents of the nonaqueous solvent, use is being made of: cycliccarbonates such as ethylene carbonate and propylene carbonate; chaincarbonates such as dimethyl carbonate, diethyl carbonate, and ethylmethyl carbonate; cyclic carboxylic acid esters such as γ-butyrolactoneand γ-valerolactone; and the like.

However, these organic solvents have volatility and are apt to catchfire. Because of this, nonaqueous-electrolyte batteries employing anelectrolyte containing any of those organic solutions in a large amountpotentially have the risk of igniting or exploding in case where thebatteries are misused or improperly used, for example, the batteries areheated, suffer internal short-circuiting or external short-circuiting,or are overcharged or overdischarged, or in case of an accident. Suchrisk is exceedingly high in large batteries intended to be usedespecially as power sources for motor vehicles.

From such standpoints, a nonaqueous electrolyte containing anambient-temperature-molten salt (also called room-temperature-moltensalt or ionic liquid) has been proposed. Although liquid, thisambient-temperature-molten salt is too low in volatility to be detected.It is also known that this salt does not burn because it does notvolatilize. Patent document 7 discloses an attempt to obtain anonaqueous-electrolyte battery having excellent safety by using theambient-temperature-molten salt as an electrolyte for lithium secondarybatteries.

Furthermore, patent document 8 discloses a technique in which anambient-temperature-molten salt having a quaternary ammonium cation andhaving excellent reductional stability is dissolved in combination witha compound, such as ethylene carbonate or vinylene carbonate, whichundergoes reductional decomposition at a nobler potential than theambient-temperature-molten salt. According to this technique, thecompound which undergoes reductional decomposition at a nobler potentialthan the ambient-temperature-molten salt electrochemically reacts in thestep of initial charge/discharge to form an electrode-protective coatingfilm on the electrode active materials, in particular, on thenegative-electrode active material, to thereby improve charge/dischargeefficiency.

-   Patent Document 1: Japanese Patent No. 3439085-   Patent Document 2: JP-A-2004-273152-   Patent Document 3: JP-A-2001-006729-   Patent Document 4: JP-A-10-050342-   Patent Document 5: JP-A-08-078053-   Patent Document 6: JP-A-11-185804-   Patent Document 7: JP-A-4-349365-   Patent Document 8: JP-A-2004-146346

DISCLOSURE OF THE INVENTION Problems that the Invention is to Solve<Nonaqueous Electrolytes 1 and 1-1, and Nonaqueous-Electrolyte SecondaryBatteries 1 and 1-1>

However, the desire for higher performances in nonaqueous-electrolytesecondary batteries is growing more and more, and it is desired toattain various characteristics including high capacity, high-temperaturestorability, continuous-charge characteristics, and cycle performanceson a high level. The prior-art technique disclosed in patent document 1,which is regarded therein as effective in improving high-temperaturestorability, has had a problem that this technique, when used alone,results in poor cycle performances especially under high-voltageconditions as will be shown by a Comparative Example given later. Anobject of inventions 1 and 1-1, which has been achieved in view of thebackground art described above, is to provide nonaqueous electrolytes 1and 1-1, which has excellent cycle performances.

<Nonaqueous Electrolyte 2 and Nonaqueous-Electrolyte Secondary Battery2>

An object of invention 2, which has been achieved in view of thebackground art described above, is to provide nonaqueous electrolyte 2for secondary batteries (nonaqueous electrolyte 2), which has excellentoutput characteristics and is excellent also in high-temperaturestorability and cycle performances.

<Nonaqueous Electrolyte 3 and Nonaqueous-Electrolyte Secondary Battery3>

An object of invention 3, which has been achieved in view of thebackground art described above, is to provide nonaqueous electrolyte 3for secondary batteries (nonaqueous electrolyte 3), which has excellentcycle performances.

<Nonaqueous Electrolyte 4 and Nonaqueous-Electrolyte Secondary Battery4>

Invention 4 has been achieved in view of the problem described above.Namely, an object of invention 4 is to provide nonaqueous electrolyte 4,which is excellent not only in low-temperature discharge characteristicsand heavy-current discharge characteristics but also in high-temperaturestorability and cycle performances and has no problem concerning safety.

<Nonaqueous Electrolyte 5 and Nonaqueous-Electrolyte Secondary Battery5>

However, the desire for higher performances in recent batteries isgrowing more and more, and it is desired to attain high capacity, highoutput, high-temperature storability, cycle performances, etc.simultaneously with high safety on a higher level.

Nonaqueous-electrolyte batteries employing the electrolyte described inpatent document 7 were insufficient in the reversibility of electrodereactions during charge/discharge and were hence unsatisfactory inbattery performances such as charge/discharge capacity, charge/dischargeefficiency, and cycle performances (see Comparative Examples 1 to 3 forInvention 5). On the other hand, a nonaqueous-electrolyte batteryemploying the electrolyte described in an Example of patent document 8,prepared by dissolving ethylene carbonate or vinylene carbonate in anambient-temperature-molten salt, has the following problem. When thebattery in a charged state is held at a temperature of 80° C. or higher,the electrode-protective coating film formed by the decomposition of theethylene carbonate or vinylene carbonate cannot inhibit theambient-temperature-molten salt from decomposing, resulting inconsiderable evolution of a decomposition gas within the battery. Theevolution of a decomposition gas within the battery increases theinternal pressure of the battery and this may cause the safety valve towork. In the case of a battery having no safety valve, there are caseswhere the battery expands due to the pressure of the gas evolved and thebattery itself becomes unusable. Furthermore, in the case where the gasevolved is flammable, there is a risk that the battery ignites orexplodes even when the nonaqueous electrolyte including anambient-temperature-molten salt has no combustibility.

As described above, in the case where the nonaqueous electrolytescontaining an ambient-temperature-molten salt which are described inpatent document 7 and patent document 8 are used, the batteries havebeen still unsatisfactory from the standpoint of reconciling batterycharacteristics and safety.

Consequently, an object of invention 5 is to reconcile an improvement incharge/discharge efficiency and the maintenance of high safety in thecase of using nonaqueous electrolyte 5, which contains anambient-temperature-molten salt.

Means for Solving the Problems <Nonaqueous Electrolytes 1 and 1-1, andNonaqueous-Electrolyte Secondary Batteries 1 and 1-1>:

The present inventors diligently made investigations in view of theproblem described above. As a result, the inventors have found that byincorporating a fluorophosphoric acid salt into a nonaqueous electrolyteand further incorporating an iron-group element in a specificconcentration, cycle performances especially under high-voltageconditions are greatly improved while maintaining high capacity.Inventions 1 and 1-1 have been thus completed.

Namely, invention 1 resides in nonaqueous electrolyte 1 which is anonaqueous electrolyte comprising a nonaqueous solvent and anelectrolyte dissolved therein, and is characterized by containing amonofluorophosphate and/or a difluorophosphate and further containing aniron-group element in an amount of 1-2, 000 ppm of the whole nonaqueouselectrolyte.

Invention 1-1 resides in nonaqueous electrolyte 1-1 which is anonaqueous electrolyte comprising a nonaqueous solvent and anelectrolyte dissolved therein, the nonaqueous electrolyte comprising: amonofluorophosphate and/or a difluorophosphate; and further aniron-group element in an amount of 0.001 ppm or more and less than 1 ppmof the whole nonaqueous electrolyte.

Invention 1-1 further resides in nonaqueous-electrolyte secondarybattery 1-1 which employs the nonaqueous electrolyte 1-1 describedabove.

Invention 1 further resides in nonaqueous-electrolyte secondary battery1 which is characterized by employing the nonaqueous electrolyte 1described above.

<Nonaqueous Electrolyte 2 and Nonaqueous-Electrolyte Secondary Battery2>:

The present inventors diligently made investigations in view of theproblem described above. As a result, the inventors have found that anonaqueous electrolyte into which a certain kind of organic compound anda specific inorganic compound have been incorporated has excellentoutput characteristics and can retain satisfactory high-temperaturestorability and satisfactory cycle performances. Invention 2 has beenthus completed.

Namely, invention 2 resides in nonaqueous electrolyte 2 which is anonaqueous electrolyte mainly comprising a nonaqueous solvent and anelectrolyte dissolved therein, and is characterized by containing atleast one compound selected from the group consisting of saturated chainhydrocarbons, saturated cyclic hydrocarbons, aromatic compounds having ahalogen atom, and ethers having a fluorine atom, and by furthercontaining a monofluorophosphate and/or a difluorophosphate.

Invention 2 further resides in nonaqueous-electrolyte secondary battery2 which is a nonaqueous-electrolyte secondary battery comprising anegative electrode and a positive electrode which are capable ofoccluding/releasing lithium ions and a nonaqueous electrolyte, and ischaracterized in that the nonaqueous electrolyte is the nonaqueouselectrolyte described above.

<Nonaqueous Electrolyte 3 and Nonaqueous-Electrolyte Secondary Battery3>:

The present inventors diligently made investigations in view of theproblem described above. As a result, the inventors have found that anonaqueous electrolyte to which a specific compound and a“monofluorophosphate and/or difluorophosphate” have been added canretain satisfactory cycle performances. Invention 3 has been thusachieved.

Namely, an essential point of invention 3 resides in nonaqueouselectrolyte 3 for secondary battery which is a nonaqueous electrolytefor use in a nonaqueous-electrolyte secondary battery comprising anegative electrode and a positive electrode which are capable ofoccluding and releasing ions and a nonaqueous electrolyte, and ischaracterized by comprising an electrolyte and a nonaqueous solvent andby further containing a monofluorophosphate and/or a difluorophosphateand containing a compound represented by the following general formula(1) and/or the following general formula (2) in a proportion of from0.001% by mass to 10% by mass based on the whole nonaqueous electrolyte:

[wherein R¹, R², R³, and R⁴ each independently are an organic group or ahalogen atom, provided that at least one of the R¹, R², R³, and R⁴ is agroup in which the atom directly bonded to the X is a heteroatom andthat two or more of the R¹, R², R³, and R⁴ may be the same; and X is anatom other than a carbon atom]

[wherein R⁵, R⁶, and R⁷ each independently are an organic group or ahalogen atom, provided that at least one of R⁵, R⁶, and R⁷ is a group inwhich the atom directly bonded to the Y is a heteroatom and that two ormore of the R⁵, R⁶, and R⁷ may be the same; and Y is an atom other thana carbon atom].

Another essential point of invention 3 resides in nonaqueous electrolyte3 for secondary battery which is a nonaqueous electrolyte for use in anonaqueous-electrolyte secondary battery comprising a negative electrodeand a positive electrode which are capable of occluding and releasingions and a nonaqueous electrolyte, and is characterized in that thenonaqueous electrolyte contains a monofluorophosphate and/or adifluorophosphate and is for use in the nonaqueous-electrolyte secondarybattery in which the positive electrode or negative electrode has beentreated with at least one compound represented by the following generalformula (1) and/or the following general formula (2):

[wherein R¹, R², R³, and R⁴ each independently are an organic group or ahalogen atom, provided that at least one of the R¹, R², R³, and R⁴ is agroup in which the atom directly bonded to the X is a heteroatom andthat two or more of the R¹, R², R³, and R⁴ may be the same; and X is anatom other than a carbon atom]

[wherein R⁵, R⁶, and R⁷ each independently are an organic group or ahalogen atom, provided that at least one of R⁵, R⁶, and R⁷ is a group inwhich the atom directly bonded to the Y is a heteroatom and that two ormore of the R⁵, R⁶, and R⁷ may be the same; and Y is an atom other thana carbon atom].

Still another essential point of invention 3 resides innonaqueous-electrolyte secondary battery 3 which is anonaqueous-electrolyte secondary battery comprising a negative electrodeand a positive electrode which are capable of occluding/releasinglithium ions and a nonaqueous electrolyte, and is characterized in thatthe nonaqueous electrolyte is the nonaqueous electrolyte 3 describedabove.

<Nonaqueous Electrolyte 4 and Nonaqueous-Electrolyte Secondary Battery4>:

The present inventors diligently made investigations in view of theproblems described above. As a result, the inventors have found that abattery which is excellent not only in low-temperature dischargecharacteristics and heavy-current discharge characteristics but also inhigh-temperature storability and cycle performances can be produced whenspecific compounds are added to a nonaqueous electrolyte. Invention 4has been thus completed.

Namely, invention 4 resides in nonaqueous electrolyte 4 which is anonaqueous electrolyte comprising a nonaqueous solvent and a lithiumsalt dissolved therein, and is characterized by containing a compoundrepresented by the following general formula (3) and further containinga monofluorophosphate and/or a difluorophosphate. Hereinafter, thisinvention is referred to as “embodiment 4-1”.

[In general formula (3), A and B each represent any of varioussubstituents, provided that at least one of the substituents representedby A and B is fluorine; and n is a natural number of 3 or larger.]

Invention 4 further resides in nonaqueous electrolyte 4 which is anonaqueous electrolyte comprising a nonaqueous solvent and a lithiumsalt dissolved therein, and is characterized by containing a compoundrepresented by the general formula (3) given above in an amount of from0.001% by mass to 5% by mass based on the whole nonaqueous electrolyteand further containing a carbonic acid ester having at least one of anunsaturated bond and a halogen atom in an amount of from 0.001% by massto 5% by mass based on the whole nonaqueous electrolyte. Hereinafter,this invention is referred to as “embodiment 4-2”.

Furthermore, invention 4 resides in nonaqueous-electrolyte secondarybattery 4 which is a nonaqueous-electrolyte secondary battery comprisinga negative electrode and a positive electrode which are capable ofoccluding/releasing lithium ions and a nonaqueous electrolyte, and ischaracterized in that the nonaqueous electrolyte is the nonaqueouselectrolyte described above.

<Nonaqueous Electrolyte 5 and Nonaqueous-Electrolyte Secondary Battery5>:

The present inventors repeatedly made various investigations in order toaccomplish the object. As a result, the inventors have found that theproblems described above can be overcome by incorporating a compoundhaving a specific structure into a nonaqueous electrolyte including anambient-temperature-molten salt. Invention 5 has been thus completed.

Namely, an essential point of invention 5 resides in nonaqueouselectrolyte 5 which is a nonaqueous electrolyte comprising a lithiumsalt and an ambient-temperature-molten salt, and is characterized bycontaining a monofluorophosphate and/or a difluorophosphate.

Another essential point of invention 5 resides in nonaqueous-electrolytebattery 5 which is a nonaqueous-electrolyte battery comprising anegative electrode and a positive electrode which are capable ofoccluding and releasing lithium ions and a nonaqueous electrolyte, andis characterized in that the nonaqueous electrolyte is the nonaqueouselectrolyte 5 described above.

ADVANTAGES OF THE INVENTION <Nonaqueous Electrolytes 1 and 1-1, andNonaqueous-Electrolyte Secondary Batteries 1 and 1-1>

According to invention 1 and invention 1-1, it is possible to providenonaqueous electrolytes 1 and 1-1 and nonaqueous-electrolyte secondarybatteries 1 and 1-1, which attain high capacity and excellent cycleperformances.

<Nonaqueous Electrolyte 2 and Nonaqueous-Electrolyte Secondary Battery2>

According to invention 2, nonaqueous electrolyte 2 can be provided,which is for use in secondary batteries excellent not only in outputcharacteristics but in high-temperature storability and cycleperformances. Nonaqueous-electrolyte secondary battery 2 can also beprovided.

<Nonaqueous Electrolyte 3 and Nonaqueous-Electrolyte Secondary Battery3>

According to invention 3, nonaqueous electrolyte 3 can be provided,which is for use in secondary batteries having excellent cycleperformances. Nonaqueous-electrolyte secondary battery 3 can also beprovided.

<Nonaqueous Electrolyte 4 and Nonaqueous-Electrolyte Secondary Battery4>

According to the nonaqueous electrolyte of invention 4,nonaqueous-electrolyte secondary battery 4 can be provided, which isexcellent not only in low-temperature discharge characteristics andheavy-current discharge characteristics but in high-temperaturestorability and cycle performances. The nonaqueous electrolyte 4 canalso be provided.

<Nonaqueous Electrolyte 5 and Nonaqueous-Electrolyte Secondary Battery5>

According to invention 5, high charge/discharge capacity andcharge/discharge efficiency which compare with those of nonaqueouselectrolytes containing ordinary nonaqueous organic solvents are madepossible while maintaining high safety, which is the most significantmerit of nonaqueous electrolytes containing anambient-temperature-molten salt. A size increase and performanceenhancement in nonaqueous-electrolyte batteries can hence be attained.

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiments of invention 1 to invention 5 (these are often referred toas “the invention”) will be explained below in detail. The followingexplanations on constituent elements are for embodiments (typicalembodiments) of the invention, and the invention should not be construedas being to the contents thereof. Various modifications of the inventioncan be made within the spirit of the invention.

<Nonaqueous Electrolyte 1 and Nonaqueous-Electrolyte Secondary Battery1> [1. Nonaqueous Electrolyte 1]

The nonaqueous electrolyte to be used in the nonaqueous-electrolytesecondary battery of invention 1 (hereinafter, this electrolyte issuitably referred to as “nonaqueous electrolyte in invention 1”) is anonaqueous electrolyte comprising a nonaqueous solvent and anelectrolyte dissolved therein, and is characterized by containing amonofluorophosphate and/or a difluorophosphate and further containing atleast one iron-group element in an amount of 1-2,000 ppm of the wholenonaqueous electrolyte.

<1-1. Electrolyte>

The electrolyte to be used in the nonaqueous electrolyte of invention 1is not limited, and known ones for use as electrolytes in a targetnonaqueous-electrolyte secondary battery can be employed andincorporated at will. In the case where the nonaqueous electrolyte ofinvention 1 is to be used in nonaqueous-electrolyte secondary batteries,the electrolyte preferably is one or more lithium salts.

Examples of the electrolyte include

-   inorganic lithium salts such as LiClO₄, LiAsF₆, LiPF₆, Li₂CO₃, and    LiBF₄;-   fluorine-containing organic lithium salts such as LiCF₃SO₃,    LiN(CF₃SO₂)₂, LiN(C₂F₅SO₂)₂, LiN(CF₃SO₂)(C₄F₉SO₂), LiC(CF₃SO₂)₃,    LiPF₄(CF₃)₂, LiPF₄(C₂F₅)₂, LiPF₄(CF₃SO₂)₂, LiPF₄(C₂F₅SO₂)₂,    LiBF₃(CF₃), LiBF₃(C₂F₅), LiBF₂(CF₃)₂, LiBF₂(C₂F₅)₂, LiBF₂(CF₃SO₂)₂,    and LiBF₂(C₂F₅SO₂)₂;-   dicarboxylic acid complex lithium salts such as lithium    bis(oxalato)borate, lithium tris(oxalato)phosphate, and lithium    difluorooxalatoborate; and-   sodium salts or potassium salts such as KPF₆, NaPF₆, NaBF₄, and    CF₃SO₃Na.

Preferred of these are LiPF₆, LiBF₄, LiCF₃SO₃, LiN(CF₃SO₂)₂,LiN(C₂F₅SO₂)₂, and lithium bis(oxalato)borate. Especially preferred isLiPF₆ or LiBF₄.

One lithium salt may be used alone, or any desired combination of two ormore lithium salts may be used in any desired proportion. In particular,a combination of two specific inorganic lithium salts or a combinationof an inorganic lithium salt and a fluorine-containing organic lithiumsalt is preferred because use of this combination is effective ininhibiting gas evolution during continuous charge or inhibitingdeterioration through high-temperature storage.

It is especially preferred to use a combination of LiPF₆ and LiBF₄ or acombination of an inorganic lithium salt, e.g., LiPF₆ or LiBF₄, and afluorine-containing organic lithium salt, e.g., LiCF₃SO₃,LiN(CF₃SO₂)_(2,) or LiN(C₂F₅SO₂)₂.

In the case where LiPF₆ and LiBF₄ are used in combination, it ispreferred that the proportion of the LiBF₄ contained should be generally0.01% by mass or higher and generally 20% by mass or lower based on allelectrolytes. LiBF₄ has a low degree of dissociation, and too highproportions thereof may result in cases where the nonaqueous electrolytehas increased resistance.

On the other hand, in the case where an inorganic lithium salt, e.g.,LiPF₆ or LiBF₄, and a fluorine-containing organic lithium salt, e.g.,LiCF₃SO₃, LiN(CF₃SO₂)₂, or LiN(C₂F₅SO₂)₂, are used in combination, it isdesirable that the proportion of the inorganic lithium salt in alllithium salts should be in the range of from generally 70% by mass togenerally 99% by mass. Since fluorine-containing organic lithium saltsgenerally have a higher molecular weight than inorganic lithium salts,too high proportions of the organic lithium salt in that combinationresults in a reduced proportion of the nonaqueous solvent in the wholenonaqueous electrolyte. There are hence cases where this nonaqueouselectrolyte has increased resistance.

The lithium salt concentration in the final composition of thenonaqueous electrolyte of invention 1 may be any desired value unlessthis concentration value considerably lessens the effect of invention 1.However, the lithium salt concentration therein is generally 0.5 mol/Lor higher, preferably 0.6 mol/L or higher, more preferably 0.8 mol/L orhigher, and is generally 3 mol/L or lower, preferably 2 mol/L or lower,more preferably 1.5 mol/L or lower. When the concentration thereof istoo low, there are cases where this nonaqueous electrolyte hasinsufficient electrical conductivity. When the concentration thereof istoo high, a viscosity increase occurs and this reduces electricalconductivity. There are hence cases where the nonaqueous-electrolytesecondary battery employing this nonaqueous electrolyte of invention 1has reduced performance.

Especially in the case where the nonaqueous solvent of the nonaqueouselectrolyte consists mainly of one or more carbonate compounds such asalkylene carbonates or dialkyl carbonates, use of LiPF₆ in combinationwith LiBF₄ is preferred although LiPF₆ may be used alone. This isbecause use of that combination inhibits capacity from deterioratingwith continuous charge. When these two salts are used in combination,the molar ratio of LiBF₄ to LiPF₆ is generally 0.005 or higher,preferably 0.01 or higher, especially preferably 0.05 or higher, and isgenerally 0.4 or lower, preferably 0.2 or lower. In case where the molarratio thereof is too high, battery characteristics tend to decreasethrough high-temperature storage. Conversely, too low molar ratiosthereof result in difficulties in obtaining the effect of inhibiting gasevolution during continuous charge or inhibiting capacity deterioration.

In the case where the nonaqueous solvent of the nonaqueous electrolyteincludes at least 50% by volume cyclic carboxylic ester compound suchas, e.g., γ-butyrolactone or γ-valerolactone, it is preferred that LiBF₄should account for 50 mol % or more of the whole first lithium salt (thelithium salt used in a highest proportion).

<1-2. Nonaqueous Solvent>

The nonaqueous solvent to be contained in the nonaqueous electrolyte ofinvention 1 is not particularly limited so long as it is a solventwhich, after used to fabricate a battery, exerts no adverse influence onthe battery characteristics. However, the nonaqueous solvent preferablyis one or more of the following solvents for use in nonaqueouselectrolytes.

Examples of nonaqueous solvents for ordinary use include chain andcyclic carbonates, chain and cyclic carboxylic acid esters, chain andcyclic ethers, phosphorus-containing organic solvents, andsulfur-containing organic solvents.

The chain carbonates are not limited in the kind thereof. Preferredexamples of chain carbonates for ordinary use include dialkylcarbonates, and the number of carbon atoms of each constituent alkylgroup is preferably 1-5, especially preferably 1-4. Examples thereofinclude dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate,methyl-n-propyl carbonate, ethyl-n-propyl carbonate, and di-n-propylcarbonate.

Of these, dimethyl carbonate, ethyl methyl carbonate, and diethylcarbonate are preferred from the standpoint of industrial availabilityand because these compounds are satisfactory in various properties in anonaqueous-electrolyte secondary battery.

The cyclic carbonates are not limited in the kind thereof. Examples ofcyclic carbonates for ordinary use include ones in which the number ofcarbon atoms of the alkylene group constituting the cyclic carbonate ispreferably 2-6, especially preferably 2-4. Specific examples thereofinclude ethylene carbonate, propylene carbonate, and butylene carbonate(2-ethylethylene carbonate or cis and trans 2,3-dimethylethylenecarbonates).

Of these, ethylene carbonate or propylene carbonate is preferred becausethese compounds are satisfactory in various properties in anonaqueous-electrolyte secondary battery.

The chain carboxylic acid esters also are not limited in the kindthereof. Examples of chain carboxylic acid esters for ordinary useinclude methyl acetate, ethyl acetate, n-propyl acetate, isopropylacetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methylpropionate, ethyl propionate, n-propyl propionate, isopropyl propionate,n-butyl propionate, isobutyl propionate, and t-butyl propionate.

Of these, ethyl acetate, methyl propionate, and ethyl propionate arepreferred from the standpoint of industrial availability and becausethese compounds are satisfactory in various properties in anonaqueous-electrolyte secondary battery.

The cyclic carboxylic acid esters also are not limited in the kindthereof. Examples of cyclic carboxylic acid esters for ordinary useinclude γ-butyrolactone, γ-valerolactone, and δ-valerolactone.

Of these, γ-butyrolactone is preferred from the standpoint of industrialavailability and because this compound is satisfactory in variousproperties in a nonaqueous-electrolyte secondary battery.

The chain ethers also are not limited in the kind thereof. Examples ofchain esters for ordinary use include dimethoxymethane, dimethoxyethane,diethoxymethane, diethoxyethane, ethoxymethoxymethane, andethoxymethoxyethane.

Of these, dimethoxyethane and diethoxyethane are preferred from thestandpoint of industrial availability and because these compounds aresatisfactory in various properties in a nonaqueous-electrolyte secondarybattery.

The cyclic ethers also are not limited in the kind thereof. Examples ofcyclic ethers for ordinary use include tetrahydrofuran,2-methyltetrahydrofuran, and tetrahydropyran.

The phosphorus-containing organic solvents also are not particularlylimited in the kind thereof. Examples of phosphorus-containing organicsolvents for ordinary use include

-   phosphoric acid esters such as trimethyl phosphate, triethyl    phosphate, and triphenyl phosphate;-   phosphorous acid esters such as trimethyl phosphite, triethyl    phosphite, and triphenyl phosphite; and-   phosphine oxides such as trimethylphosphine oxide, triethylphosphine    oxide, and triphenylphosphine oxide.

Furthermore, the sulfur-containing organic solvents also are notparticularly limited in the kind thereof. Examples of sulfur-containingorganic solvents for ordinary use include ethylene sulfite,1,3-propanesultone, 1,4-butanesultone, methyl methanesulfonate,busulfan, sulfolane, sulfolene, dimethyl sulfone, diphenyl sulfone,methyl phenyl sulfone, dibutyl disulfide, dicyclohexyl disulfide,tetramethylthiuram monosulfide, N,N-dimethylmethanesulfonamide, andN,N-diethylmethanesulfonamide.

Of those compounds, the chain and cyclic carbonates or the chain andcyclic carboxylic acid esters are preferred because these compounds aresatisfactory in various properties in a nonaqueous-electrolyte secondarybattery. More preferred of these are ethylene carbonate, propylenecarbonate, dimethyl carbonate, ethyl methyl carbonate, diethylcarbonate, ethyl acetate, methyl propionate, ethyl propionate, andγ-butyrolactone. Even more preferred are ethylene carbonate, propylenecarbonate, dimethyl carbonate, ethyl methyl carbonate, diethylcarbonate, ethyl acetate, methyl propionate, and γ-butyrolactone.

Those compounds may be used alone or in combination of two or morethereof. It is, however, preferred to use two or more compounds incombination. For example, it is preferred to use a high-permittivitysolvent, such as a cyclic carbonate, in combination with a low-viscositysolvent, such as a chain carbonate or a chain ester.

A preferred combination of nonaqueous solvents is a combinationconsisting mainly of at least one cyclic carbonate and at least onechain carbonate. Especially preferred is such a combination in which thetotal proportion of the cyclic carbonate and the chain carbonate to thewhole nonaqueous solvent is 80% by volume or higher, preferably 85% byvolume or higher, more preferably 90% by volume or higher, and theproportion by volume of the cyclic carbonate to the sum of the cycliccarbonate and the chain carbonate is 5% by volume or higher, preferably10% by volume or higher, more preferably 15% by volume or higher, and isgenerally 50% by volume or lower, preferably 35% by volume or lower,more preferably 30% by volume or lower. Use of such combination ofnonaqueous solvents is preferred because the battery fabricated withthis combination has an improved balance between cycle performances andhigh-temperature storability (in particular, residual capacity andhigh-load discharge capacity after high-temperature storage).

Examples of the preferred combination including at least one cycliccarbonate and at least one chain carbonate include: ethylene carbonateand dimethyl carbonate; ethylene carbonate and diethyl carbonate;ethylene carbonate and ethyl methyl carbonate; ethylene carbonate,dimethyl carbonate, and diethyl carbonate; ethylene carbonate, dimethylcarbonate, and ethyl methyl carbonate; ethylene carbonate, diethylcarbonate, and ethyl methyl carbonate; and ethylene carbonate, dimethylcarbonate, diethyl carbonate, and ethyl methyl carbonate.

Combinations obtained by further adding propylene carbonate to thosecombinations including ethylene carbonate and one or more chaincarbonates are also included in preferred combinations. In the casewhere propylene carbonate is contained, the volume ratio of the ethylenecarbonate to the propylene carbonate is preferably from 99:1 to 40:60,especially preferably from 95:5 to 50:50. It is also preferred toregulate the proportion of the propylene carbonate to the wholenonaqueous solvent to a value which is 0.1% by volume or higher,preferably 1% by volume or higher, more preferably 2% by volume orhigher, and is generally 10% by volume or lower, preferably 8% by volumeor lower, more preferably 5% by volume or lower. This is because thisregulation brings about excellent discharge load characteristics whilemaintaining the properties of the combination of ethylene carbonate andone or more chain carbonates.

More preferred of these are combinations including an asymmetric chaincarbonate. In particular, combinations including ethylene carbonate, asymmetric chain carbonate, and an asymmetric chain carbonate, such as acombination of ethylene carbonate, dimethyl carbonate, and ethyl methylcarbonate, a combination of ethylene carbonate, diethyl carbonate, andethyl methyl carbonate, and a combination of ethylene carbonate,dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate, orsuch combinations which further contain propylene carbonate arepreferred because these combinations have a satisfactory balance betweencycle performances and discharge load characteristics. Preferred of suchcombinations are ones in which the asymmetric chain carbonate is ethylmethyl carbonate. Furthermore, the number of carbon atoms of each of thealkyl groups constituting each dialkyl carbonate is preferably 1-2.

Other examples of preferred mixed solvents are ones containing a chainester. In particular, the cyclic carbonate/chain carbonate mixedsolvents which contain a chain ester are preferred from the standpointof improving the discharge load characteristics of a battery. The chainester especially preferably is ethyl acetate or methyl propionate. Theproportion by volume of the chain ester to the nonaqueous solvent isgenerally 5% or higher, preferably 8% or higher, more preferably 15% orhigher, and is generally 50% or lower, preferably 35% or lower, morepreferably 30% or lower, even more preferably 25% or lower.

Other preferred examples of the nonaqueous solvent are ones in which oneorganic solvent selected from the group consisting of ethylenecarbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, andγ-valerolactone or a mixed solvent composed of two or more organicsolvents selected from the group accounts for at least 60% by volume ofthe whole. Such mixed solvents have a flash point of preferably 50° C.or higher, especially preferably 70° C. or higher. The nonaqueouselectrolyte employing this solvent is reduced in solvent vaporizationand liquid leakage even when used at high temperatures. In particular,when such a nonaqueous solvent which includes ethylene carbonate andγ-butyrolactone in a total amount of 80% by volume or larger, preferably90% by volume or larger, based on the nonaqueous solvent and in whichthe volume ratio of the ethylene carbonate to the γ-butyrolactone isfrom 5:95 to 45:55 or such a nonaqueous solvent which includes ethylenecarbonate and propylene carbonate in a total amount of 80% by volume orlarger, preferably 90% by volume or larger, based on the nonaqueoussolvent and in which the volume ratio of the ethylene carbonate to thepropylene carbonate is from 30:70 to 80:20 is used, then an improvedbalance between cycle performances and discharge load characteristics,etc. is generally obtained.

<1-3. Monofluorophosphate and Difluorophosphate>

The nonaqueous electrolyte of invention 1 contains a monofluorophosphateand/or a difluorophosphate as an essential component. The“monofluorophosphate and/or difluorophosphate” to be used in invention 1is not particularly limited in the kind thereof so long as thisingredient is constituted of one or more monofluorophosphate ions and/ordifluorophosphate ions and one or more cations. However, this ingredientmust be selected in view of the necessity of finally producing anonaqueous electrolyte usable as the electrolyte of anonaqueous-electrolyte secondary battery to be used.

It is therefore preferred that the monofluorophosphate and/ordifluorophosphate in invention 1 should be a salt of one or moremonofluorophosphate ions and/or difluorophosphate ions with one or moreions of at least one metal selected from Group 1, Group 2, and Group 13of the periodic table (hereinafter these metal ions are suitablyreferred to as “specific metal ions”) or with a quaternary onium. Themonofluorophosphate and/or difluorophosphate may be one salt or may beany desired combination of two or more salts.

<1-3-1. Monofluorophosphoric Acid Metal Salt and Difluorophosphoric AcidMetal Salt>

First, an explanation is given on the case where the monofluorophosphateand difluorophosphate in invention 1 are a salt of one or moremonofluorophosphate ions or one or more difluorophosphate ions with oneor more specific metal ions (hereinafter sometimes referred to as“monofluorophosphoric acid metal salt” and “difluorophosphoric acidmetal salt”, respectively).

Examples of the metals in Group 1 of the periodic table among thespecific metals usable in the monofluorophosphoric acid metal salt anddifluorophosphoric acid metal salt in invention 1 include lithium,sodium, potassium, and cesium. Preferred of these is lithium or sodium.Lithium is especially preferred.

Examples of the metals in Group 2 of the periodic table includemagnesium, calcium, strontium, and barium. Preferred of these ismagnesium or calcium. Magnesium is especially preferred.

Examples of the metals in Group 13 of the periodic table includealuminum, gallium, indium, and thallium. Preferred of these is aluminumor gallium. Aluminum is especially preferred.

The number of the atoms of such a specific metal possessed by onemolecule of the monofluorophosphoric acid metal salt ordifluorophosphoric acid metal salt in invention 1 is not limited. Thesalt may have only one atom of the specific metal or two or more atomsthereof.

In the case where the monofluorophosphoric acid metal salt or thedifluorophosphoric acid metal salt in invention 1 has two or more atomsof a specific metal per molecule, these specific-metal atoms may be ofthe same kind or may be of different kinds. Besides the specificmetal(s), one or more atoms of a metal other than the specific metalsmaybe possessed.

Examples of the monofluorophosphoric acid metal salt anddifluorophosphoric acid metal salt include Li₂PO₃F, Na₂PO₃F, MgPO₃F,CaPO₃F, Al₂(PO₃F)₃, Ga₂(PO₃F)₃, LiPO₂F₂, NaPO₂F₂, Mg (PO₂F₂)₂,Ca(PO₂F₂)₂, Al(PO₂F₂)_(3r) and Ga₂(PO₂F₂)₃. Preferred of these areLi₂PO₃F, LiPO₂F₂, NaPO₂F₂, and Mg(PO₂F₂)₂.

<1-3-2. Monofluorophosphoric Acid Quaternary Onium Salt andDifluorophosphoric Acid Quaternary Onium Salt>

An explanation is then given on the case where the monofluorophosphateand difluorophosphate in invention 1 are a salt of a monofluorophosphateion or difluorophosphate ion with a quaternary onium (hereinaftersometimes referred to as “monofluorophosphoric acid quaternary oniumsalt” and “difluorophosphoric acid quaternary onium salt”,respectively).

The quaternary onium used in the monofluorophosphoric acid quaternaryonium salt and difluorophosphoric acid quaternary onium salt ininvention 1 usually is a cation. Examples thereof include cationsrepresented by the following general formula (4).

In general formula (4), R^(1m) to R^(4m) each independently represent ahydrocarbon group. The kind of this hydrocarbon group is not limited.Namely, the hydrocarbon group may be an aliphatic hydrocarbon group oran aromatic hydrocarbon group, or maybe a hydrocarbon group includingthese two kinds of groups bonded to each other. In the case of analiphatic hydrocarbon group, this group may be a chain or cyclic groupor may be a structure including a chain moiety and a cyclic moietybonded thereto. In the case of a chain hydrocarbon group, this group maybe linear or branched. The hydrocarbon group may be a saturatedhydrocarbon group or may have one or more unsaturated bonds.

Examples of the hydrocarbon groups represented by R^(1m) to R^(4m)include alkyl groups, cycloalkyl groups, aryl groups, and aralkylgroups.

Examples of the alkyl groups include methyl, ethyl, 1-propyl,1-methylethyl, 1-butyl, 1-methylpropyl, 2-methylpropyl, and1,1-dimethylethyl.

Preferred of these are methyl, ethyl, 1-propyl, 1-butyl, and the like.

Examples of the cycloalkyl groups include cyclopentyl,2-methylcyclopentyl, 3-methylcyclopentyl, 2,2-dimethylcyclopentyl,2,3-dimethylcyclopentyl, 2,4-dimethylcyclopentyl,2,5-dimethylcyclopentyl, 3,3-dimethylcyclopentyl,3,4-dimethylcyclopentyl, 2-ethylcyclopentyl, 3-ethylcyclopentyl,cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl,2,2-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl,2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl,3,5-dimethylcyclohexyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl,4-ethylcyclohexyl, bicyclo[3.2.1]oct-1-yl, and bicyclo[3.2.1]oct-2-yl.

Preferred of these are cyclopentyl, 2-methylcyclopentyl,3-methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl,4-methylcyclohexyl, and the like.

Examples of the aryl groups include phenyl, 2-methylphenyl,3-methylphenyl, 4-methylphenyl, and 2,3-dimethylphenyl.

Preferred of these is phenyl.

Examples of the aralkyl groups include phenylmethyl, 1-phenylethyl,2-phenylethyl, diphenylmethyl, and triphenylmethyl.

Preferred of these are phenylmethyl and 2-phenylethyl.

The hydrocarbon groups represented by R^(1m) to R^(4m) each may havebeen substituted with one or more substituents. The kinds of thesubstituents are not limited unless the substituents considerably lessenthe effects of invention 1. Examples of the substituents include halogenatoms, hydroxyl, amino, nitro, cyano, carboxyl, ether groups, andaldehyde groups. In the case where the hydrocarbon group represented byeach of R^(1m) to R^(4m) has two or more substituents, thesesubstituents maybe the same or different.

When any two or more of the hydrocarbon groups represented by R^(1m) toR^(4m) are compared, the hydrocarbon groups may be the same ordifferent. When the hydrocarbon groups represented by R^(1m) to R^(9m)have a substituent, these substituted hydrocarbon groups including thesubstituents maybe the same or different. Furthermore, any desired twoor more of the hydrocarbon groups represented by R^(1m) to R^(4m) mayhave been bonded to each other to form a cyclic structure.

The number of carbon atoms of each of the hydrocarbon groups representedby R^(1m) to R^(4m) is generally 1 or larger, and the upper limitthereof is generally 20 or smaller, preferably 10 or smaller, morepreferably 5 or smaller. When the number of carbon atoms thereof is toolarge, the number of moles per unit mass is too small and variouseffects tend to be reduced. In the case where the hydrocarbon grouprepresented by each of R^(1m) to R^(4m) has substituents, the number ofcarbon atoms of the substituted hydrocarbon group including thesesubstituents is generally within that range.

In general formula (4), Q represents an atom belonging to Group 15 ofthe periodic table. Preferred of such atoms is a nitrogen atom orphosphorus atom.

In view of the above explanation, preferred examples of the quaternaryonium represented by general formula (4) include aliphatic chainquaternary salts, alicyclic ammoniums, alicyclic phosphoniums, andnitrogen-containing heterocyclic aromatic cations.

Especially preferred of the aliphatic chain quaternary salts aretetraalkylammoniums, tetraalkylphosphoniums, and the like.

Examples of the tetraalkylammoniums include tetramethylammonium,ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium,tetraethylammonium, and tetra-n-butylammonium.

Examples of the tetraalkylphosphoniums include tetramethylphosphonium,ethyltrimethylphosphonium, diethyldimethylphosphonium,triethylmethylphosphonium, tetraethylphosphonium, andtetra-n-butylphosphonium.

Especially preferred of the alicyclic ammoniums are pyrrolidiniums,morpholiniums, imidazoliniums, tetrahydropyrimidiniums, piperaziniums,piperidiniums, and the like.

Examples of the pyrrolidiniums include N,N-dimethylpyrrolidium,N-ethyl-N-methylpyrrolidium, and N,N-diethylpyrrolidium.

Examples of the morpholiniums include N,N-dimethylmorpholinium,N-ethyl-N-methylmorpholinium, and N,N-diethylmorpholinium.

Examples of the imidazoliniums include N,N′-dimethylimidazolinium,N-ethyl-N′-methylimidazolinium, N,N′-diethylimidazolinium, and1,2,3-trimethylimidazolinium.

Examples of the tetrahydropyrimidiniums includeN,N′-dimethyltetrahydropyrimidinium,N-ethyl-N′-methyltetrahydropyrimidinium,N,N′-diethyltetrahydropyrimidinium, and1,2,3-trimehyltetrahydropyrimidinium.

Examples of the piperaziniums include N,N,N′,N′-tetramethylpiperazinium,N-ethyl-N,N′,N′-trimethylpiperazinium,N,N-diethyl-N′,N′-dimethylpiperazinium,N,N,N′-triethyl-N′-methylpiperazinium, andN,N,N′,N′-tetraethylpiperazinium.

Examples of the piperidiniums include N,N-dimethylpiperidinium,N-ethyl-N-methylpiperidinium, and N,N-diethylpiperidinium.

Especially preferred of the nitrogen-containing heterocyclic aromaticcations are pyridiniums, imidazoliums, and the like.

Examples of the pyridiniums include N-methylpyridinium,N-ethylpyridinium, 1,2-dimethylpyrimidinium, 1,3-dimethylpyrimidinium,1,4-dimethylpyrimidinium, and 1-ethyl-2-methylpyrimidinium.

Examples of the imidazoliums include N,N′-dimethylimidazolium,N-ethyl-N′-methylimidazolium, N,N′-diethylimidazolium, and1,2,3-trimethylimidazolium.

Namely, the salts of the quaternary oniums enumerated above with themonofluorophosphate ions and/or difluorophosphate ions enumerated aboveare preferred examples of the monofluorophosphoric acid quaternary oniumsalt and difluorophosphoric acid quaternary onium salt in invention 1.

<1-3-3. Content, Detection (Derivation of Containment), Technical Range,Etc.>

In the nonaqueous electrolyte of invention 1, one monofluorophosphate ordifluorophosphate only may be used or any desired combination of two ormore monofluorophosphates and/or difluorophosphates may be used in anydesired proportion. However, from the standpoint of efficientlyoperating the nonaqueous-electrolyte secondary battery, it is preferredto use one monofluorophosphate or difluorophosphate.

The molecular weight of the monofluorophosphate or difluorophosphate isnot limited, and may be any desired value unless this considerablylessens the effects of invention 1. However, the molecular weightthereof is generally 100 or higher. There is no particular upper limiton the molecular weight thereof. However, it is preferred that themolecular weight thereof should be generally 1,000 or lower, preferably500 or lower, because such a value is practicable in view of thereactivity of this reaction.

Processes for producing the monofluorophosphate and thedifluorophosphate also are not particularly limited, and known processesselected at will can be used to produce the salts.

The proportion of the monofluorophosphate and difluorophosphate in thenonaqueous electrolyte is preferably 10 ppm or higher (0.001% by mass orhigher), more preferably 0.01% by mass or higher, especially preferably0.05% by mass or higher, even more preferably 0.1% by mass or higher, interms of the total content of the salts based on the whole nonaqueouselectrolyte. The upper limit of the proportion of the sum of the saltsis preferably 5% by mass or lower, more preferably 4% by mass or lower,even more preferably 3% by mass or lower. When the concentration of themonofluorophosphate and the difluorophosphate is too low, there arecases where the effect of improving discharge load characteristics isdifficult to obtain. On the other hand, too high concentrations thereofmay lead to a decrease in charge/discharge efficiency.

When a nonaqueous electrolyte containing a monofluorophosphate and adifluorophosphate is subjected to the actual fabrication of anonaqueous-electrolyte secondary battery and the battery is disassembledto discharge the nonaqueous electrolyte again, then there are oftencases where the content of the salts in this nonaqueous electrolyte hasdecreased considerably. Consequently, the nonaqueous electrolytedischarged from a battery can be regarded as included in invention 1when at least one monofluorophosphate and/or difluorophosphate can bedetected in the electrolyte even in a slight amount. Furthermore, evenwhen a nonaqueous electrolyte containing a monofluorophosphate and adifluorophosphate is subjected to the actual fabrication of anonaqueous-electrolyte secondary battery and the nonaqueous electrolyterecovered by disassembling this battery and discharging the nonaqueouselectrolyte therefrom does not contain the monofluorophosphate and/ordifluorophosphate, then there are often cases where the phosphoric acidsalt is detected on the positive electrode, negative electrode, orseparator as another constituent member of the nonaqueous-electrolytesecondary battery. Consequently, when at least one monofluorophosphateand/or difluorophosphate has been detected in at least one constituentmember selected from the positive electrode, negative electrode, andseparator, this case also is regarded as included in invention 1.

Moreover, when a monofluorophosphate and/or a difluorophosphate has beenincorporated into a nonaqueous electrolyte and has further beenincorporated into at least one constituent member selected from thepositive electrode, negative electrode, and separator, this case also isregarded as included in invention 1.

On the other hand, a monofluorophosphate and/or a difluorophosphatemaybe incorporated beforehand into an inner part or the surface of thepositive electrode of a nonaqueous-electrolyte secondary battery to befabricated. In this case, part or the whole of the monofluorophosphateand/or difluorophosphate which has been incorporated beforehand isexpected to dissolve in the nonaqueous electrolyte to perform thefunction thereof. This case also is regarded as included in invention 1.

Techniques for incorporating the salt beforehand into an inner part of apositive electrode or into the surface of a positive electrode are notparticularly limited. Examples thereof include: a method in which amonofluorophosphate and/or a difluorophosphate is dissolved beforehandin a slurry to be prepared in the production of a positive electrodewhich will be described later; and a method in which a solution preparedby dissolving a monofluorophosphate and/or a difluorophosphate in anydesired nonaqueous solvent beforehand is applied to or infiltrated intoa positive electrode which has been produced, and this electrode isdried to remove the solvent used and thereby incorporate the salt.

Furthermore, use may be made of a method in which anonaqueous-electrolyte secondary battery is actually fabricated using anonaqueous electrolyte containing at least one monofluorophosphateand/or difluorophosphate so that the salt is incorporated into an innerpart of the positive electrode or the surface of the positive electrodefrom the nonaqueous electrolyte. Since the nonaqueous electrolyte isinfiltrated into the positive electrode in fabricating anonaqueous-electrolyte secondary battery, there are often cases wherethe monofluorophosphate and difluorophosphate are contained in an innerpart of the positive electrode or in the surface of the positiveelectrode. Because of this, when at least a monofluorophosphate and/or adifluorophosphate can be detected in the positive electrode recoveredfrom a disassembled battery, this case is regarded as included ininvention 1.

A monofluorophosphate and a difluorophosphate may be incorporatedbeforehand into an inner part or the surface of the negative electrodeof a nonaqueous-electrolyte secondary battery to be fabricated. In thiscase, part or the whole of the monofluorophosphate and/ordifluorophosphate which has been incorporated beforehand is expected todissolve in the nonaqueous electrolyte to perform the function thereof.This case is regarded as included in invention 1. Techniques forincorporating the salt beforehand into an inner part of a negativeelectrode or into the surface of a negative electrode are notparticularly limited. Examples thereof include: a method in which amonofluorophosphate and a difluorophosphate are dissolved beforehand ina slurry to be prepared in the production of a negative electrode whichwill be described later; and a method in which a solution prepared bydissolving a monofluorophosphate and a difluorophosphate in any desirednonaqueous solvent beforehand is applied to or infiltrated into anegative electrode which has been produced, and this electrode is driedto remove the solvent used and thereby incorporate the salt.

Furthermore, use may be made of a method in which anonaqueous-electrolyte secondary battery is actually fabricated using anonaqueous electrolyte containing at least one monofluorophosphate anddifluorophosphate so that the salt is incorporated into an inner part ofthe negative electrode or the surface of the negative electrode from thenonaqueous electrolyte. Since the nonaqueous electrolyte is infiltratedinto the negative electrode in fabricating a nonaqueous-electrolytesecondary battery, there are often cases where the monofluorophosphateand difluorophosphate are contained in an inner part of the negativeelectrode or in the surface of the negative electrode. Because of this,when at least a monofluorophosphate and a difluorophosphate can bedetected in the negative electrode recovered from a disassembledbattery, this case is regarded as included in invention 1.

A monofluorophosphate and/or a difluorophosphate may also beincorporated beforehand into an inner part or the surface of theseparator of a nonaqueous-electrolyte secondary battery to befabricated. In this case, part or the whole of the monofluorophosphateand difluorophosphate which have been incorporated beforehand isexpected to dissolve in the nonaqueous electrolyte to perform thefunction thereof. This case is regarded as included in invention 1.Techniques for incorporating the salts beforehand into an inner part ofa separator or into the surface of a separator are not particularlylimited. Examples thereof include: a method in which amonofluorophosphate and a difluorophosphate are mixed beforehand duringseparator production; and a method in which a solution prepared bydissolving a monofluorophosphate and a difluorophosphate in any desirednonaqueous solvent beforehand is applied to or infiltrated into aseparator to be subjected to the fabrication of a nonaqueous-electrolytesecondary battery, and this separator is dried to remove the solventused and thereby incorporate the salt.

Furthermore, use may be made of a method in which anonaqueous-electrolyte secondary battery is actually fabricated using anonaqueous electrolyte containing a monofluorophosphate and/or adifluorophosphate so that the salt is incorporated into an inner part ofthe separator or the surface of the separator from the nonaqueouselectrolyte. Since the nonaqueous electrolyte is infiltrated into theseparator in fabricating a nonaqueous-electrolyte secondary battery,there are often cases where the monofluorophosphate anddifluorophosphate are contained in an inner part of the separator or inthe surface of the separator. Because of this, when at least amonofluorophosphate and a difluorophosphate can be detected in theseparator recovered from a disassembled battery, this case is regardedas included in invention 1.

<1-4. Iron-Group Element>

The nonaqueous electrolyte of invention 1 further contains at least oneiron-group element in a specific concentration besides themonofluorophosphate and/or difluorophosphate described above. Thecoexistence of the monofluorophosphate and/or difluorophosphate ofinvention 1 with an iron-group element contained in a specificconcentration produces a synergistic effect, whereby cycle performancesespecially under the conditions of a high voltage exceeding 4.2 V, whichis the upper-limit use voltage of ordinary nonaqueous-electrolytesecondary batteries, can be greatly improved.

Factors in the production of such synergistic effect have not beenelucidated in detail. Although the scope of invention 1 is not construedas being limited by the factors, the following is thought. Cations ofthe iron-group element are incorporated into a product of the reductionreaction of the “monofluorophosphate and/or difluorophosphate”, which isan essential component of the nonaqueous electrolyte of invention 1, toform an ionomer such as, e.g., one having P—O-M-O—P bonds (wherein Mrepresents the iron-group element). A stabler protective coating film ispresumed to be thus formed. It is thought that to cause the nonaqueouselectrolyte to contain an iron-group element in the stage of initialcharge, in which a coating film is formed, is effective in forming sucha protective coating film.

<1-4-1. Kind of Iron-Group Element>

The “iron-group element” to be contained in the nonaqueous electrolytein invention 1 specifically means any of iron element, cobalt element,and nickel element. Of these, cobalt element and nickel element arepreferred from the standpoint of forming a stabler coating film.

With respect to techniques for incorporating an iron-group element intoa nonaqueous electrolyte in invention 1, it is preferred to dissolve aniron-group element compound in the nonaqueous electrolyte. As the“iron-group element compound” in invention 1, it is generally preferredto use an ionic compound in which the iron-group element has anoxidation number of +2 or +3.

Examples of the “iron-group element compound” includehexafluorophosphoric acid salts such as iron(II) hexafluorophosphate,iron(III) hexafluorophosphate, cobalt(II) hexafluorophosphate, andnickel(II) hexafluorophosphate; tetrafluoroboric acid salts such asiron(II) tetrafluoroborate, iron(III) tetrafluoroborate, cobalt(II)tetrafluoroborate, and nickel(II) tetrafluoroborate; perchloric acidsalts such as iron(II) perchlorate, iron(III) perchlorate, cobalt(II)perchlorate, and nickel(II) perchlorate; sulfuric acid salts such asiron (II) sulfate, iron (III) sulfate, cobalt(II) sulfate, andnickel(II) sulfate; nitric acid salts such as iron(II) nitrate,iron(III) nitrate, cobalt(II) nitrate, and nickel(II) nitrate; aceticacid salts such as iron(II) acetate, iron(III) acetate, cobalt(II)acetate, and nickel(II) acetate; carbonic acid salts such as iron(II)carbonate, iron(III) carbonate, cobalt(II) carbonate, and nickel(II)carbonate; oxalic acid salts such as iron(II) oxalate, iron(III)oxalate, cobalt(II) oxalate, and nickel(II) oxalate; citric acid saltssuch as iron(II) citrate, iron(III) citrate, cobalt(II) citrate, andnickel(II) citrate; benzoic acid salts such as iron(II) benzoate,iron(III) benzoate, cobalt(II) benzoate, and nickel(II) benzoate;phosphoric acid salts such as iron(II) phosphate, iron(III) phosphate,cobalt(II) phosphate, and nickel(II) phosphate; fluorides such asiron(II) fluoride, iron(III) fluoride, cobalt(II) fluoride, andnickel(II) fluoride; and iron-group element acetylacetonates such asiron(II) acetylacetonate, iron(III) acetylacetonate, cobalt(II)acetylacetonate, cobalt(III) acetylacetonate, and nickel(II)acetylacetonate.

Preferred of these are the following salts constituted of one or moreanions less apt to react in batteries and of cobalt or nickel:hexafluorophosphoric acid salts such as cobalt(II) hexafluorophosphateand nickel(II) hexafluorophosphate; tetrafluoroboric acid salts such ascobalt(II) tetrafluoroborate and nickel(II) tetrafluoroborate;perchloric acid salts such as cobalt(II) perchlorate and nickel(II)perchlorate; phosphoric acid salts such as cobalt(II) phosphate andnickel(II) phosphate; and fluorides such as cobalt(II) fluoride andnickel(II) fluoride.

Of these, hexafluorophosphoric acid salts such as cobalt(II)hexafluorophosphate and nickel(II) hexafluorophosphate and fluoridessuch as cobalt(II) fluoride and nickel(II) fluoride are more preferredbecause these compounds are stable in batteries. These iron-groupelement compounds may be used alone or in any desired combination of twoor more thereof. It is preferred that those iron-group element compoundsshould be anhydrides. However, even when the compounds are hydrates,they can be used so long as the dehydration which will be describedlater is conducted.

<1-4-2. Content and Method of Determining the Same>

The content of the iron-group element in invention 1 is generally 1 ppmor higher, preferably 2 ppm or higher, more preferably 3 ppm or higher,especially preferably 5 ppm or higher, most preferably 8 ppm or higher,and is generally 2,000 ppm or lower, preferably 600 ppm or lower, morepreferably 100 ppm or lower, especially preferably 50 ppm or lower, mostpreferably 30 ppm or lower, based on the whole nonaqueous electrolyte.When the content thereof is lower than the lower limit of that range,there are cases where the effect of invention 1 described above ishardly produced. When the content thereof exceeds the upper limit, thereare cases where the iron-group element is apt to be reduced at thenegative electrode to deposit as the metal on the negative electrode.Furthermore, there are cases where the iron-group element present in toolarge an amount induces the decomposition of the electrolyte, resultingin reduced cycle performances. Incidentally, in the case where two ormore iron-group elements of invention 1 are used in combination, theseiron-group elements are used so that the total concentration thereof iswithin that range.

Although an iron-group element may be added in invention 1, aniron-group element may have been generated in the electrolyte. In thecase where an iron-group element has been generated in the electrolyte,the content of the iron-group element in the nonaqueous electrolyte canbe determined by an ordinary method of metallic-element analysis, suchas, e.g., atomic absorption spectrometry (AAS), inductively coupledplasma spectroscopy (ICP), or X-ray fluorescence analysis (XRF). Inparticular, ICP spectroscopy is suitable because a pretreatment thereforis easy and the analysis has high accuracy and is less apt to beinfluenced by other elements.

<1-5. Additives>

The nonaqueous electrolyte of invention 1 may contain various additivesso long as these additives do not considerably lessen the effects ofinvention 1. In the case where additives are additionally incorporatedto prepare the nonaqueous electrolyte, conventionally known additivescan be used at will. One additive may be used alone, or any desiredcombination of two or more additives in any desired proportion may beused.

Examples of the additives include overcharge inhibitors and aids forimproving capacity retention after high-temperature storage and cycleperformances. It is preferred to add a carbonate having at least one ofan unsaturated bond and a halogen atom (hereinafter sometimes referredto as “specific carbonate”) as an aid for improving capacity retentionafter high-temperature storage and cycle performances, among thoseadditives. The specific carbonate and other additives are separatelyexplained below.

<1-5-1. Specific Carbonate>

The specific carbonate is a carbonate having at least one of anunsaturated bond and a halogen atom. The specific carbonate may have oneor more unsaturated bonds only or have one or more halogen atoms only,or may have both one or more unsaturated bonds and one or more halogenatoms.

The molecular weight of the specific carbonate is not particularlylimited, and may be any desired value unless this considerably lessensthe effects of invention 1. However, the molecular weight thereof isgenerally 50 or higher, preferably 80 or higher, and is generally 250 orlower, preferably 150 or lower. When the molecular weight thereof is toohigh, this specific carbonate has reduced solubility in the nonaqueouselectrolyte and there are cases where the effect of the carbonate isdifficult to produce sufficiently.

Processes for producing the specific carbonate also are not particularlylimited, and a known process selected at will can be used to produce thecarbonate.

Anyone specific carbonate maybe incorporated alone into the nonaqueouselectrolyte of invention 1, or any desired combination of two or morespecific carbonates may be incorporated thereinto in any desiredproportion.

The amount of the specific carbonate to be incorporated into thenonaqueous electrolyte of invention 1 is not limited, and may be anydesired value unless this considerably lessens the effects ofinvention 1. It is, however, desirable that the specific carbonateshould be incorporated in a concentration which is generally 0.01% bymass or higher, preferably 0.1% by mass or higher, more preferably 0.3%by mass or higher, and is generally 70% by mass or lower, preferably 50%by mass or lower, more preferably 40% by mass or lower, based on thenonaqueous electrolyte of invention 1.

When the amount of the specific carbonate is below the lower limit ofthat range, there are cases where use of this nonaqueous electrolyte ofinvention 1 in a nonaqueous-electrolyte secondary battery results indifficulties in producing the effect of sufficiently improving the cycleperformances of the nonaqueous-electrolyte secondary battery. On theother hand, when the proportion of the specific carbonate is too high,there is a tendency that use of this nonaqueous electrolyte of invention1 in a nonaqueous-electrolyte secondary battery results in decreases inthe high-temperature storability and continuous-charge characteristicsof the nonaqueous-electrolyte secondary battery. In particular, thereare cases where gas evolution is enhanced and capacity retentiondecreases.

(1-5-1-1. Unsaturated Carbonate)

The carbonate having one or more unsaturated bonds (hereinafter oftenreferred to as “unsaturated carbonate”) as one form of the specificcarbonate according to invention 1 is not limited so long as it is acarbonate having one or more carbon-carbon unsaturated bonds, such ascarbon-carbon double bonds or carbon-carbon triple bonds, and anydesired unsaturated carbonate can be used. Incidentally, carbonateshaving one or more aromatic rings are also included in the carbonatehaving one or more unsaturated bonds.

Examples of the unsaturated carbonate include vinylene carbonate andderivatives thereof, ethylene carbonate derivatives substituted with oneor more aromatic rings or with one or more substituents having acarbon-carbon unsaturated bond, phenyl carbonates, vinyl carbonates, andallyl carbonates.

Examples of the vinylene carbonate and derivatives thereof includevinylene carbonate, methylvinylene carbonate, 4,5-dimethylvinylenecarbonate, phenylvinylene carbonate, 4,5-diphenylvinylene carbonate, andcatechol carbonate.

Examples of the ethylene carbonate derivatives substituted with one ormore aromatic rings or with one or more substituents having acarbon-carbon unsaturated bond include vinylethylene carbonate,4,5-divinylethylene carbonate, phenylethylene carbonate, and4,5-diphenylethylene carbonate.

Examples of the phenyl carbonates include diphenyl carbonate, ethylphenyl carbonate, methyl phenyl carbonate, and t-butyl phenyl carbonate.

Examples of the vinyl carbonates include divinyl carbonate and methylvinyl carbonate.

Examples of the allyl carbonates include diallyl carbonate and allylmethyl carbonate.

Preferred of these unsaturated carbonates as examples of the specificcarbonate are the vinylene carbonate and derivatives thereof and theethylene carbonate derivatives substituted with one or more aromaticrings or with one or more substituents having a carbon-carbonunsaturated bond. In particular, vinylene carbonate,4,5-diphenylvinylene carbonate, 4,5-dimethylvinylene carbonate, andvinylethylene carbonate are more preferred because these carbonates forma stable interface-protective coating film.

(1-5-1-2. Halogenated Carbonate)

On the other hand, the carbonate having one or more halogen atoms(hereinafter often referred to as “halogenated carbonate”) as one formof the specific carbonate according to invention 1 is not particularlylimited so long as it is a carbonate having one or more halogen atoms,and any desired halogenated carbonate can be used.

Examples of the halogen atoms include fluorine, chlorine, bromine, andiodine atoms. Preferred of these are fluorine atoms or chlorine atoms.Especially preferred are fluorine atoms. The number of halogen atomspossessed by the halogenated carbonate also is not particularly limitedso long as the number thereof is 1 or larger. However, the numberthereof is generally 6 or smaller, preferably 4 or smaller. In the casewhere the halogenated carbonate has two or more halogen atoms, theseatoms may be the same or different.

Examples of the halogenated carbonate include ethylene carbonatederivatives, dimethyl carbonate derivatives, ethyl methyl carbonatederivatives, and diethyl carbonate derivatives.

Examples of the ethylene carbonate derivatives include fluoroethylenecarbonate, chloroethylene carbonate, 4,4-difluoroethylene carbonate,4,5-difluoroethylene carbonate, 4,4-dichloroethylene carbonate,4,5-dichloroethylene carbonate, 4-fluoro-4-methylethylene carbonate,4-chloro-4-methylethylene carbonate, 4,5-difluoro-4-methylethylenecarbonate, 4,5-dichloro-4-methylethylene carbonate,4-fluoro-5-methylethylene carbonate, 4-chloro-5-methylethylenecarbonate, 4,4-difluoro-5-methylethylene carbonate,4,4-dichloro-5-methylethylene carbonate, 4-(fluoromethyl)-ethylenecarbonate, 4-(chloromethyl)-ethylene carbonate,4-(difluoromethyl)-ethylene carbonate, 4-(dichloromethyl)-ethylenecarbonate, 4-(trifluoromethyl)-ethylene carbonate,4-(trichloromethyl)-ethylene carbonate,4-(fluoromethyl)-4-fluoroethylene carbonate,4-(chloromethyl)-4-chloroethylene carbonate,4-(fluoromethyl)-5-fluoroethylene carbonate,4-(chloromethyl)-5-chloroethylene carbonate,4-fluoro-4,5-dimethylethylene carbonate, 4-chloro-4,5-dimethylethylenecarbonate, 4,5-difluoro-4,5-dimethylethylene carbonate,4,5-dichloro-4,5-dimethylethylene carbonate,4,4-difluoro-5,5-dimethylethylene carbonate, and4,4-dichloro-5,5-dimethylethylene carbonate.

Examples of the dimethyl carbonate derivatives include fluoromethylmethyl carbonate, difluoromethyl methyl carbonate, trifluoromethylmethyl carbonate, bis(fluoromethyl) carbonate, bis(difluoromethyl)carbonate, bis(trifluoromethyl) carbonate, chloromethyl methylcarbonate, dichloromethyl methyl carbonate, trichloromethyl methylcarbonate, bis(chloromethyl) carbonate, bis(dichloro)methyl carbonate,and bis(trichloro)methyl carbonate.

Examples of the ethyl methyl carbonate derivatives include 2-fluoroethylmethyl carbonate, ethyl fluoromethyl carbonate, 2,2-difluoroethyl methylcarbonate, 2-fluoroethyl fluoromethyl carbonate, ethyl difluoromethylcarbonate, 2,2,2-trifluoroethyl methyl carbonate, 2,2-difluoroethylfluoromethyl carbonate, 2-fluoroethyl difluoromethyl carbonate, ethyltrifluoromethyl carbonate, 2-chloroethyl methyl carbonate, ethylchloromethyl carbonate, 2,2-dichloroethyl methyl carbonate,2-chloroethyl chloromethyl carbonate, ethyl dichloromethyl carbonate,2,2,2-trichloroethyl methyl carbonate, 2,2-dichloroethyl chloromethylcarbonate, 2-chloroethyl dichloromethyl carbonate, and ethyltrichloromethyl carbonate.

Examples of the diethyl carbonate derivatives includeethyl-(2-fluoroethyl) carbonate, ethyl-(2,2-difluoroethyl) carbonate,bis(2-fluoroethyl) carbonate, ethyl-(2,2,2-trifluoroethyl) carbonate,2,2-difluoroethyl-2′-fluoroethyl carbonate, bis(2,2-difluoroethyl)carbonate, 2,2,2-trifluoroethyl-2′-fluoroethyl carbonate,2,2,2-trifluoroethyl-2′,2′-difluoroethyl carbonate,bis(2,2,2-trifluoroethyl) carbonate, ethyl-(2-chloroethyl) carbonate,ethyl-(2,2-dichloroethyl) carbonate, bis(2-chloroethyl) carbonate,ethyl-(2,2,2-trichloroethyl) carbonate, 2,2-dichloroethyl-2′-chloroethylcarbonate, bis(2,2-dichloroethyl) carbonate,2,2,2-trichloroethyl-2′-chloroethyl carbonate,2,2,2-trichloroethyl-2′,2′-dichloroethyl carbonate, andbis(2,2,2-trichloroethyl) carbonate.

Preferred of these halogenated carbonates are the carbonates having oneor more fluorine atoms. More preferred are the ethylene carbonatederivatives having one or more fluorine atoms. In particular,fluoroethylene carbonate, 4-(fluoromethyl)-ethylene carbonate,4,4-difluoroethylene carbonate, and 4,5-difluoroethylene carbonate aremore suitable because these carbonates form an interface-protectivecoating film.

(1-5-1-3. Halogenated Unsaturated Carbonate)

Furthermore usable as the specific carbonate is a carbonate having bothone or more unsaturated bonds and one or more halogen atoms (thiscarbonate is suitably referred to as “halogenated unsaturatedcarbonate”). This halogenated unsaturated carbonate is not particularlylimited, and any desired halogenated unsaturated carbonate can be usedunless the effects of invention 1 are considerably lessened thereby.

Examples of the halogenated unsaturated carbonate include vinylenecarbonate derivatives, ethylene carbonate derivatives substituted withone or more aromatic rings or with one or more substituents having acarbon-carbon unsaturated bond, and allyl carbonates.

Examples of the vinylene carbonate derivatives include fluorovinylene,4-fluoro-5-methylvinylene carbonate, 4-fluoro-5-phenylvinylenecarbonate, 4-(trifluoromethyl)vinylene carbonate, chlorovinylenecarbonate, 4-chloro-5-methylvinylene carbonate,4-chloro-5-phenylvinylene carbonate, and 4-(trichloromethyl)vinylenecarbonate.

Examples of the ethylene carbonate derivatives substituted with one ormore aromatic rings or with one or more substituents having acarbon-carbon unsaturated bond include 4-fluoro-4-vinylethylenecarbonate, 4-fluoro-5-vinylethylene carbonate,4,4-difluoro-5-vinylethylene carbonate, 4,5-difluoro-4-vinylethylenecarbonate, 4-chloro-5-vinylethylene carbonate,4,4-dichloro-5-vinylethylene carbonate, 4,5-dichloro-4-vinylethylenecarbonate, 4-fluoro-4,5-divinylethylene carbonate,4,5-difluoro-4,5-divinylethylene carbonate, 4-chloro-4,5-divinylethylenecarbonate, 4,5-dichloro-4,5-divinylethylene carbonate,4-fluoro-4-phenylethylene carbonate, 4-fluoro-5-phenylethylenecarbonate, 4,4-difluoro-5-phenylethylene carbonate,4,5-difluoro-4-phenylethylene carbonate, 4-chloro-4-phenylethylenecarbonate, 4-chloro-5-phenylethylene carbonate,4,4-dichloro-5-phenylethylene carbonate, 4,5-dichloro-4-phenylethylenecarbonate, 4,5-difluoro-4,5-diphenylethylene carbonate, and4,5-dichloro-4,5-diphenylethylene carbonate.

Examples of phenyl carbonates include fluoromethyl phenyl carbonate,2-fluoroethyl phenyl carbonate, 2,2-difluoroethyl phenyl carbonate,2,2,2-trifluoroethyl phenyl carbonate, chloromethyl phenyl carbonate,2-chloroethyl phenyl carbonate, 2,2-dichloroethyl phenyl carbonate, and2,2,2-trichloroethyl phenyl carbonate.

Examples of vinyl carbonates include fluoromethyl vinyl carbonate,2-fluoroethyl vinyl carbonate, 2,2-difluoroethyl vinyl carbonate,2,2,2-trifluoroethyl vinyl carbonate, chloromethyl vinyl carbonate,2-chloroethyl vinyl carbonate, 2,2-dichloroethyl vinyl carbonate, and2,2,2-trichloroethyl vinyl carbonate.

Examples of the allyl carbonates include fluoromethyl allyl carbonate,2-fluoroethyl allyl carbonate, 2,2-difluoroethyl allyl carbonate,2,2,2-trifluoroethyl allyl carbonate, chloromethyl allyl carbonate,2-chloroethyl allyl carbonate, 2,2-dichloroethyl allyl carbonate, and2,2,2-trichloroethyl allyl carbonate.

It is especially preferred to use, as the specific carbonate, one ormore members selected from the group consisting of vinylene carbonate,vinylethylene carbonate, fluoroethylene carbonate, 4,5-difluoroethylenecarbonate, and derivatives of these, among the examples of thehalogenated unsaturated carbonate enumerated above. These preferredcarbonates are highly effective when used alone.

<1-5-2. Other Additives>

Additives other than the specific carbonate are explained below.Examples of the additives other than the specific carbonate includeovercharge inhibitors and aids for improving capacity retention afterhigh-temperature storage and cycle performances.

<1-5-2-1. Overcharge Inhibitors>

Examples of the overcharge inhibitors include aromatic compoundsincluding:

-   toluene and derivatives thereof, such as toluene and xylene;-   unsubstituted biphenyl or alkyl-substituted biphenyl derivatives,    such as biphenyl, 2-methylbiphenyl, 3-methylbiphenyl, and    4-methylbiphenyl;-   unsubstituted terphenyls or alkyl-substituted terphenyl derivatives,    such as o-terphenyl, m-terphenyl, and p-terphenyl;-   partly hydrogenated unsubstituted terphenyls or partly hydrogenated    alkyl-substituted terphenyl derivatives;-   cycloalkylbenzenes and derivatives thereof, such as    cyclopentylbenzene and cyclohexylbenzene;-   alkylbenzene derivatives having one or more tertiary carbon atoms    directly bonded to the benzene ring, such as cumene,    1,3-diisopropylbenzene, and 1,4-diisopropylbenzene;-   alkylbenzene derivatives having a quaternary carbon atom directly    bonded to the benzene ring, such as t-butylbenzene, t-amylbenzene,    and t-hexylbenzene; and-   aromatic compounds having an oxygen atom, such as diphenyl ether and    dibenzofuran.

Other examples of the overcharge inhibitors include products of thepartial fluorination of aromatic compounds shown above, such asfluorobenzene, fluorotoluene, benzotrifluoride, 2-fluorobiphenyl,o-cyclohexylfluorobenzene, and p-cyclohexylfluorobenzene; andfluorine-containing anisole compounds such as 2,4-difluoroanisole,2,5-difluoroanisole, and 1,6-difluoroanisole.

One of those overcharge inhibitors may be used alone, or any desiredcombination of two or more thereof may be used in any desiredproportion. In the case of employing any desired combination, compoundsin the same class among those enumerated above may be used incombination or compounds in different classes may be used incombination.

Examples of the case where compounds indifferent classes are used incombination include:

-   a toluene derivative and a biphenyl derivative;-   a toluene derivative and a terphenyl derivative;-   a toluene derivative and a partly hydrogenated terphenyl derivative;-   a toluene derivative and a cycloalkylbenzene derivative;-   a toluene derivative and an alkylbenzene derivative having one or    more tertiary carbon atoms directly bonded to the benzene ring;-   a toluene derivative and an alkylbenzene derivative having a    quaternary carbon atom directly bonded to the benzene ring;-   a toluene derivative and an aromatic compound having an oxygen atom;-   a toluene derivative and a partly fluorinated aromatic compound;-   a toluene derivative and a fluorine-containing anisole compound;-   a biphenyl derivative and a terphenyl derivative;-   a biphenyl derivative and a partly hydrogenated terphenyl    derivative;-   a biphenyl derivative and a cycloalkylbenzene derivative;-   a biphenyl derivative and an alkylbenzene derivative having one or    more tertiary carbon atoms directly bonded to the benzene ring;-   a biphenyl derivative and an alkylbenzene derivative having a    quaternary carbon atom directly bonded to the benzene ring;-   a biphenyl derivative and an aromatic compound having an oxygen    atom;-   a biphenyl derivative and a partly fluorinated aromatic compound;-   a biphenyl derivative and a fluorine-containing anisole compound;-   a terphenyl derivative and a partly hydrogenated terphenyl    derivative;-   a terphenyl derivative and a cycloalkylbenzene derivative;-   a terphenyl derivative and an alkylbenzene derivative having one or    more tertiary carbon atoms directly bonded to the benzene ring;-   a terphenyl derivative and an alkylbenzene derivative having a    quaternary carbon atom directly bonded to the benzene ring;-   a terphenyl derivative and an aromatic compound having an oxygen    atom;-   a terphenyl derivative and a partly fluorinated aromatic compound;-   a terphenyl derivative and a fluorine-containing anisole compound;-   a partly hydrogenated terphenyl derivative and a cycloalkylbenzene    derivative;-   a partly hydrogenated terphenyl derivative and an alkylbenzene    derivative having one or more tertiary carbon atoms directly bonded    to the benzene ring;-   a partly hydrogenated terphenyl derivative and an alkylbenzene    derivative having a quaternary carbon atom directly bonded to the    benzene ring;-   a partly hydrogenated terphenyl derivative and an aromatic compound    having an oxygen atom;-   a partly hydrogenated terphenyl derivative and a partly fluorinated    aromatic compound;-   a partly hydrogenated terphenyl derivative and a fluorine-containing    anisole compound;-   a cycloalkylbenzene derivative and an alkylbenzene derivative having    one or more tertiary carbon atoms directly bonded to the benzene    ring;-   a cycloalkylbenzene derivative and an alkylbenzene derivative having    a quaternary carbon atom directly bonded to the benzene ring;-   a cycloalkylbenzene derivative and an aromatic compound having an    oxygen atom;-   a cycloalkylbenzene derivative and a partly fluorinated aromatic    compound;-   a cycloalkylbenzene derivative and a fluorine-containing anisole    compound;-   an alkylbenzene derivative having one or more tertiary carbon atoms    directly bonded to the benzene ring and an alkylbenzene derivative    having a quaternary carbon atom directly bonded to the benzene ring;-   an alkylbenzene derivative having one or more tertiary carbon atoms    directly bonded to the benzene ring and an aromatic compound having    an oxygen atom;-   an alkylbenzene derivative having one or more tertiary carbon atoms    directly bonded to the benzene ring and a partly fluorinated    aromatic compound;-   an alkylbenzene derivative having one or more tertiary carbon atoms    directly bonded to the benzene ring and a fluorine-containing    anisole compound;-   an alkylbenzene derivative having a quaternary carbon atom directly    bonded to the benzene ring and an aromatic compound having an oxygen    atom;-   an alkylbenzene derivative having a quaternary carbon atom directly    bonded to the benzene ring and a partly fluorinated aromatic    compound;-   an alkylbenzene derivative having a quaternary carbon atom directly    bonded to the benzene ring and a fluorine-containing anisole    compound;-   an aromatic compound having an oxygen atom and a partly fluorinated    aromatic compound;-   an aromatic compound having an oxygen atom and a fluorine-containing    anisole compound; and-   a partly fluorinated aromatic compound and a fluorine-containing    anisole compound.

Specific examples thereof include a combination of biphenyl ando-terphenyl, a combination of biphenyl and m-terphenyl, a combination ofbiphenyl and a partly hydrogenated terphenyl derivative, a combinationof biphenyl and cumene, a combination of biphenyl andcyclopentylbenzene, a combination of biphenyl and cyclohexylbenzene, acombination of biphenyl and t-butylbenzene, a combination of biphenyland t-amylbenzene, a combination of biphenyl and diphenyl ether, acombination of biphenyl and dibenzofuran, a combination of biphenyl andfluorobenzene, a combination of biphenyl and benzotrifluoride, acombination of biphenyl and 2-fluorobiphenyl, a combination of biphenyland o-fluorocyclohexylbenzene, a combination of biphenyl andp-fluorocyclohexylbenzene, a combination of biphenyl and2,4-difluoroanisole,

-   a combination of o-terphenyl and a partly hydrogenated terphenyl    derivative, a combination of o-terphenyl and cumene, a combination    of o-terphenyl and cyclopentylbenzene, a combination of o-terphenyl    and cyclohexylbenzene, a combination of o-terphenyl and    t-butylbenzene, a combination of o-terphenyl and t-amylbenzene, a    combination of o-terphenyl and diphenyl ether, a combination of    o-terphenyl and dibenzofuran, a combination of o-terphenyl and    fluorobenzene, a combination of o-terphenyl and benzotrifluoride, a    combination of o-terphenyl and 2-fluorobiphenyl, a combination of    o-terphenyl and o-fluorocyclohexylbenzene, a combination of    o-terphenyl and p-fluorocyclohexylbenzene, a combination of    o-terphenyl and 2,4-difluoroanisole,-   a combination of m-terphenyl and a partly hydrogenated terphenyl    derivative, a combination of m-terphenyl and cumene, a combination    of m-terphenyl and cyclopentylbenzene, a combination of m-terphenyl    and cyclohexylbenzene, a combination of m-terphenyl and    t-butylbenzene, a combination of m-terphenyl and t-amylbenzene, a    combination of m-terphenyl and diphenyl ether, a combination of    m-terphenyl and dibenzofuran, a combination of m-terphenyl and    fluorobenzene, a combination of m-terphenyl and benzotrifluoride, a    combination of m-terphenyl and 2-fluorobiphenyl, a combination of    m-terphenyl and o-fluorocyclohexylbenzene, a combination of    m-terphenyl and p-fluorocyclohexylbenzene, a combination of    m-terphenyl and 2,4-difluoroanisole,-   a combination of a partly hydrogenated terphenyl derivative and    cumene, a combination of a partly hydrogenated terphenyl derivative    and cyclopentylbenzene, a combination of a partly hydrogenated    terphenyl derivative and cyclohexylbenzene, a combination of a    partly hydrogenated terphenyl derivative and t-butylbenzene, a    combination of a partly hydrogenated terphenyl derivative and    t-amylbenzene, a combination of a partly hydrogenated terphenyl    derivative and diphenyl ether, a combination of a partly    hydrogenated terphenyl derivative and dibenzofuran, a combination of    a partly hydrogenated terphenyl derivative and fluorobenzene, a    combination of a partly hydrogenated terphenyl derivative and    benzotrifluoride, a combination of a partly hydrogenated terphenyl    derivative and 2-fluorobiphenyl, a combination of a partly    hydrogenated terphenyl derivative and o-fluorocyclohexylbenzene, a    combination of a partly hydrogenated terphenyl derivative and    p-fluorocyclohexylbenzene, a combination of a partly hydrogenated    terphenyl derivative and 2,4-difluoroanisole,-   a combination of cumene and cyclopentylbenzene, a combination of    cumene and cyclohexylbenzene, a combination of cumene and    t-butylbenzene, a combination of cumene and t-amylbenzene, a    combination of cumene and diphenyl ether, a combination of cumene    and dibenzofuran, a combination of cumene and fluorobenzene, a    combination of cumene and benzotrifluoride, a combination of cumene    and 2-fluorobiphenyl, a combination of cumene and    o-fluorocyclohexylbenzene, a combination of cumene and    p-fluorocyclohexylbenzene, a combination of cumene and    2,4-difluoroanisole,-   a combination of cyclohexylbenzene and t-butylbenzene, a combination    of cyclohexylbenzene and t-amylbenzene, a combination of    cyclohexylbenzene and diphenyl ether, a combination of    cyclohexylbenzene and dibenzofuran, a combination of    cyclohexylbenzene and fluorobenzene, a combination of    cyclohexylbenzene and benzotrifluoride, a combination of    cyclohexylbenzene and 2-fluorobiphenyl, a combination of    cyclohexylbenzene and o-fluorocyclohexylbenzene, a combination of    cyclohexylbenzene and p-fluorocyclohexylbenzene, a combination of    cyclohexylbenzene and 2,4-difluoroanisole,-   a combination of t-butylbenzene and t-amylbenzene, a combination of    t-butylbenzene and diphenyl ether, a combination of t-butylbenzene    and dibenzofuran, a combination of t-butylbenzene and fluorobenzene,    a combination of t-butylbenzene and benzotrifluoride, a combination    of t-butylbenzene and 2-fluorobiphenyl, a combination of    t-butylbenzene and o-fluorocyclohexylbenzene, a combination of    t-butylbenzene and p-fluorocyclohexylbenzene, a combination of    t-butylbenzene and 2,4-difluoroanisole,-   a combination of t-amylbenzene and diphenyl ether, a combination of    t-amylbenzene and dibenzofuran, a combination of t-amylbenzene and    fluorobenzene, a combination of t-amylbenzene and benzotrifluoride,    a combination of t-amylbenzene and 2-fluorobiphenyl, a combination    of t-amylbenzene and o-fluorocyclohexylbenzene, a combination of    t-amylbenzene and p-fluorocyclohexylbenzene, a combination of    t-amylbenzene and 2,4-difluoroanisole,-   a combination of diphenyl ether and dibenzofuran, a combination of    diphenyl ether and fluorobenzene, a combination of diphenyl ether    and benzotrifluoride, a combination of diphenyl ether and    2-fluorobiphenyl, a combination of diphenyl ether and    o-fluorocyclohexylbenzene, a combination of diphenyl ether and    p-fluorocyclohexylbenzene, a combination of diphenyl ether and    2,4-difluoroanisole,-   a combination of dibenzofuran and fluorobenzene, a combination of    dibenzofuran and benzotrifluoride, a combination of dibenzofuran and    2-fluorobiphenyl, a combination of dibenzofuran and    o-fluorocyclohexylbenzene, a combination of dibenzofuran and    p-fluorocyclohexylbenzene, a combination of dibenzofuran and    2,4-difluoroanisole,-   a combination of fluorobenzene and benzotrifluoride, a combination    of fluorobenzene and 2-fluorobiphenyl, a combination of    fluorobenzene and o-fluorocyclohexylbenzene, a combination of    fluorobenzene and p-fluorocyclohexylbenzene, a combination of    fluorobenzene and 2,4-difluoroanisole,-   a combination of benzotrifluoride and 2-fluorobiphenyl, a    combination of benzotrifluoride and o-fluorocyclohexylbenzene, a    combination of benzotrifluoride and p-fluorocyclohexylbenzene, a    combination of benzotrifluoride and 2,4-difluoroanisole,-   a combination of 2-fluorobiphenyl and o-fluorocyclohexylbenzene, a    combination of 2-fluorobiphenyl and p-fluorocyclohexylbenzene, a    combination of 2-fluorobiphenyl and 2,4-difluoroanisole,-   a combination of o-fluorocyclohexylbenzene and    p-fluorocyclohexylbenzene, a combination of    o-fluorocyclohexylbenzene and 2,4-difluoroanisole, and a combination    of p-fluorocyclohexylbenzene and 2,4-difluoroanisole.

In the case where the nonaqueous electrolyte of invention 1 contains anovercharge inhibitor, the concentration thereof may be any value unlessthis considerably lessens the effects of invention 1. It is, however,desirable that the concentration thereof should be regulated so as to bein the range of generally from 0.1% by mass to 5% by mass based on thewhole nonaqueous electrolyte.

To incorporate an overcharge inhibitor into the nonaqueous electrolyteof invention 1 in such an amount as not to considerably lessen theeffects of invention 1 is preferred because the nonaqueous-electrolytesecondary battery has improved safety even if overcharged due to anerroneous usage or under a situation in which an overcharge protectioncircuit does not work normally, such as, e.g., charger abnormality.

<1-5-2-2. Aids>

On the other hand, examples of the aids for improving capacity retentionafter high-temperature storage and cycle performances include theanhydrides of dicarboxylic acids such as succinic acid, maleic acid, andphthalic acid;

-   carbonate compounds other than the specific carbonates, such as    erythritan carbonate and spiro-bis-dimethylene carbonate;-   sulfur-containing compounds such as ethylene sulfite,    1,3-propanesultone, 1,4-butanesultone, methyl methanesulfonate,    busulfan, sulfolane, sulfolene, dimethyl sulfone, diphenyl sulfone,    methyl phenyl sulfone, dibutyl disulfide, dicyclohexyl disulfide,    tetramethylthiuram monosulfide, N,N-dimethylmethanesulfonamide, and    N,N-diethylmethanesulfonamide;-   nitrogen-containing compounds such as 1-methyl-2-pyrrolidinone,    1-methyl-2-piperidone, 3-methyl-2-oxazolidinone,    1,3-dimethyl-2-imidazolidinone, and N-methylsuccinimide;-   hydrocarbon compounds such as heptane, octane, and cycloheptane; and-   fluorine-containing aromatic compounds such as fluorobenzene,    difluorobenzene, and benzotrifluoride.

<1-6. Process for Producing Nonaqueous Electrolyte>

The nonaqueous electrolyte in invention 1 can be prepared by dissolvingan electrolyte and the “monofluorophosphate and/or difluorophosphate”and “iron-group element compound” according to invention 1 in anonaqueous solvent optionally together with “other aids”.

It is preferred that in preparing the nonaqueous electrolyte, each ofthe raw materials for the nonaqueous electrolyte, i.e., the lithiumsalt, monofluorophosphate and/or difluorophosphate and iron-groupelement compound according to invention 1, nonaqueous organic solvent,and other aids, should be dehydrated beforehand. With respect to thedegree of dehydration, it is desirable to dehydrate each raw material togenerally 50 ppm or lower, preferably 30 ppm or lower. In thisdescription, ppm means proportion by mass.

When water is present in the nonaqueous electrolyte, there is apossibility that electrolysis of the water, reaction of the water withlithium metal, hydrolysis of the lithium salt, etc. might occur. Thepresence of water is hence undesirable. Techniques for the dehydrationare not particularly limited. However, in the case where the material tobe dehydrated is, for example, a liquid, e.g., a nonaqueous solvent, amolecular sieve or the like may be used. In the case where the materialto be dehydrated is a solid, e.g., an electrolyte, this material may bedried at a temperature lower than decomposition temperatures. In thecase where the iron-group element compound is a hydrate, use may be madeof a method in which the iron-group element compound is dissolved in anonaqueous solvent and the resultant solution is dehydrated with amolecular sieve or the like.

[2. Nonaqueous-Electrolyte Secondary Battery]

The nonaqueous-electrolyte secondary battery of invention 1 includes: anegative electrode and a positive electrode which are capable ofoccluding and releasing ions; and the nonaqueous electrolyte ofinvention 1 described above.

<2-1. Battery Constitution>

The constitution of the nonaqueous-electrolyte secondary battery ofinvention 1, excluding the negative electrode and the nonaqueouselectrolyte, may be the same as that of conventionally knownnonaqueous-electrolyte secondary batteries. Usually, the battery ofinvention 1 has a constitution including a positive electrode and anegative electrode which have been superposed through a porous film(separator) impregnated with the nonaqueous electrolyte of invention 1,the electrodes and the separator being held in a case. Consequently, theshape of the nonaqueous-electrolyte secondary battery of invention 1 isnot particularly limited, and may be any of the cylindrical type,prismatic type, laminate type, coin type, large type, and the like.

<2-2. Nonaqueous Electrolyte>

As the nonaqueous electrolyte, the nonaqueous electrolyte of invention 1described above is used. Incidentally, a mixture of the nonaqueouselectrolyte of invention 1 and another nonaqueous electrolyte may beused so long as this is not counter to the spirit of invention 1.

<2-3. Negative Electrode>

Negative-electrode active materials usable in the negative electrode aredescribed below. The negative-electrode active materials are notparticularly limited so long as these are capable of electrochemicallyoccluding/releasing lithium ions. Examples thereof include acarbonaceous material, an alloy material, and a lithium-containing metalcomposite oxide material.

<2-3-1. Carbonaceous Material>

The carbonaceous material to be used as a negative-electrode activematerial preferably is one which is selected from: (1) naturalgraphites; (2) artificial carbonaceous substances and carbonaceousmaterials obtained by subjecting artificial graphitic substances to aheat treatment at a temperature in the range of 400-3,200° C. one ormore times; (3) carbonaceous materials giving a negative-electrodeactive-material layer which is composed of at least two carbonaceoussubstances differing in crystallinity and/or has an interface where atleast two carbonaceous substances differing in crystallinity are incontact with each other; and (4) carbonaceous materials giving anegative-electrode active-material layer which is composed of at leasttwo carbonaceous substances differing in orientation and/or has aninterface where at least two carbonaceous substances differing inorientation are in contact with each other. This is because thiscarbonaceous material brings about a satisfactory balance betweeninitial irreversible capacity and high-current-density charge/dischargecharacteristics. One of the carbonaceous materials (1) to (4) may beused alone, or any desired combination of two or more thereof in anydesired proportion may be used.

Examples of the artificial carbonaceous substances and artificialgraphitic substances in (2) above include natural graphites, coal coke,petroleum coke, coal pitch, petroleum pitch, carbonaceous substancesobtained by oxidizing these pitches, needle coke, pitch coke, carbonmaterials obtained by partly graphitizing these cokes, products of thepyrolysis of organic substances, such as furnace black, acetylene black,and pitch-derived carbon fibers, organic substances capable ofcarbonization and products of the carbonization thereof, or solutionsobtained by dissolving any of such organic substances capable ofcarbonization in a low-molecular organic solvent, e.g., benzene,toluene, xylene, quinoline, or n-hexane, and products of thecarbonization of these solutions.

Examples of the organic substances capable of carbonization include coaltar pitches ranging from soft pitch to hard pitch, coal-derived heavyoil such as dry distillation/liquefaction oil, straight-run heavy oilsuch as topping residues and vacuum distillation residues, heavy oilsresulting from petroleum cracking, such as ethylene tar as a by-productof the thermal cracking of crude oil, naphtha, etc., aromatichydrocarbons such as acenaphthylene, decacyclene, anthracene, andphenanthrene, nitrogen-atom-containing heterocyclic compounds such asphenazine and acridine, sulfur-atom-containing heterocyclic compoundssuch as thiophene and bithiophene, polyphenylenes such as biphenyl andterphenyl, poly(vinyl chloride), poly(vinyl alcohol), poly(vinylbutyral), substances obtained by insolubilizing these compounds,nitrogen-containing organic polymers such as polyacrylonitrile andpolypyrrole, sulfur-containing organic polymers such as polythiophene,organic polymers such as polystyrene, natural polymers such aspolysaccharides represented by cellulose, lignin, mannan,poly(galacturonic acid), chitosan, and saccharose, thermoplastic resinssuch as poly(phenylene sulfide) and poly(phenylene oxide), andthermosetting resins such as furfuryl alcohol resins,phenol-formaldehyde resins, and imide resins.

<2-3-2. Constitution and Properties of Carbonaceous Negative Electrodeand Method of Preparation thereof>

With respect to the properties of the carbonaceous material, negativeelectrode containing the carbonaceous material, method of electrodeformation, current collector, and nonaqueous-electrolyte secondarybattery, it is desirable that any one of the following (1) to (18)should be satisfied or two or more thereof be simultaneously satisfied.

(1) X-Ray Parameter

The carbonaceous material preferably has a value of d (interplanarspacing) for the lattice planes (002), as determined by X-raydiffractometry in accordance with the method of the Japan Society forPromotion of Scientific Research, of generally 0.335-0.340 nm,especially 0.335-0.338 nm, in particular 0.335-0.337 nm. The crystallitesize (Lc) thereof, as determined by X-ray diffractometry in accordancewith the method of the Japan Society for Promotion of ScientificResearch, is generally 1.0 nm or larger, preferably 1.5 nm or larger,especially preferably 2 nm or larger.

A preferred material obtained by coating the surface of a graphite withamorphous carbon is one which is constituted of a graphite having avalue of d for the lattice planes (002) as determined by X-raydiffractometry of 0.335-0.338 nm as a core material and, adherent to thesurface thereof, a carbonaceous material having a larger value of d forthe lattice planes (002) as determined by X-ray diffractometry than thecore material, and in which the proportion of the core material to thecarbonaceous material having a larger value of d for the lattice planes(002) as determined by X-ray diffractometry than the core material isfrom 99/1 to 80/20 in terms of weight ratio. By using this material, anegative electrode which has a high capacity and is less apt to reactwith the electrolyte can be produced.

(2) Ash Content

The ash content of the carbonaceous material is preferably 1% by mass orlower, especially 0.5% by mass or lower, in particular 0.1% by mass orlower, based on the whole carbonaceous material. The lower limit of theash content thereof is preferably at least 1 ppm by mass of the wholecarbonaceous material. When the ash content by mass thereof exceeds theupper limit of that range, there are cases where battery performancedeterioration caused by reaction with the nonaqueous electrolyte duringcharge/discharge becomes not negligible. When the ash content thereof islower than the lower limit of that range, there are cases where theproduction of this carbonaceous material necessitates much time andenergy and an apparatus for pollution prevention, resulting in anincrease in cost.

(3) Volume-Average Particle Diameter

With respect to the volume-average particle diameter of the carbonaceousmaterial, the volume-average particle diameter (median diameter) thereofas determined by the laser diffraction/scattering method is generally 1μm or larger, preferably 3 μm or larger, more preferably 5 μm or larger,especially preferably 7 μm or larger, and is generally 100 μm orsmaller, preferably 50 μm or smaller, more preferably 40 μm or smaller,even more preferably 30 μm or smaller, especially preferably 25 μm orsmaller. When the volume-average particle diameter thereof is smallerthan the lower limit of that range, there are cases where irreversiblecapacity increases, leading to a loss in initial battery capacity. Whenthe volume-average particle diameter thereof exceeds the upper limit ofthat range, there are cases where such a carbonaceous material isundesirable from the standpoint of battery production because an unevencoating surface is apt to result when an electrode is produced throughcoating fluid application.

Volume-average particle diameter is determined by dispersing the carbonpowder in a 0.2% by mass aqueous solution (about 10 mL) ofpoly(oxyethylene (20)) sorbitan monolaurate as a surfactant andexamining the dispersion with a laser diffraction/scattering typeparticle size distribution analyzer (LA-700, manufactured by HORIBA,Ltd.). The median diameter determined through this measurement isdefined as the volume-average particle diameter of the carbonaceousmaterial in invention 1.

(4) Raman R Value, Raman Half-Value Width

The Raman R value of the carbonaceous material as determined by theargon ion laser Raman spectroscopy is generally 0.01 or higher,preferably 0.03 or higher, more preferably 0.1 or higher, and isgenerally 1.5 or lower, preferably 1.2 or lower, more preferably 1 orlower, especially preferably 0.5 or lower.

When the Raman R value thereof is lower than the lower limit of thatrange, the surface of such particles has too high crystallinity andthere are cases where the number of intercalation sites into whichlithium comes with charge/discharge decreases. Namely, there are caseswhere suitability for charge decreases. In addition, when a coatingfluid containing such a carbonaceous material is applied to a currentcollector and the resultant coating is pressed to heighten the densityof the negative electrode, then the crystals are apt to orient indirections parallel to the electrode plate and this may lead to adecrease in load characteristics. On the other hand, when the Raman Rvalue thereof exceeds the upper limit of that range, the surface of suchparticles has reduced crystallinity and enhanced reactivity with thenonaqueous electrolyte and this may lead to a decrease in efficiency andenhanced gas evolution.

The Raman half-value width around 1,580 cm⁻¹ of the carbonaceousmaterial is not particularly limited. However, the half-value widththereof is generally 10 cm⁻¹ or larger, preferably 15 cm⁻¹ or larger,and is generally 100 cm⁻¹ or smaller, preferably 80 cm⁻¹ or smaller,more preferably 60 cm⁻¹ or smaller, especially preferably 40 cm⁻¹ orsmaller.

When the Raman half-value width thereof is smaller than the lower limitof that range, the surface of such particles has too high crystallinityand there are cases where the number of intercalation sites into whichlithium comes with charge/discharge decreases. Namely, there are caseswhere suitability for charge decreases. In addition, when a coatingfluid containing such a carbonaceous material is applied to a currentcollector and the resultant coating is pressed to heighten the densityof the negative electrode, then the crystals are apt to orient indirections parallel to the electrode plate and this may lead to adecrease in load characteristics. On the other hand, when the Ramanhalf-value width thereof exceeds the upper limit of that range, thesurface of such particles has reduced crystallinity and enhancedreactivity with the nonaqueous electrolyte and this may lead to adecrease in efficiency and enhanced gas evolution.

The examination for a Raman spectrum is made with a Raman spectrometer(Raman spectrometer manufactured by Japan Spectroscopic Co., Ltd.). Inthe examination, a sample is charged into a measuring cell by causingthe sample to fall naturally into the cell and the surface of the samplein the cell is irradiated with argon ion laser light while rotating thecell in a plane perpendicular to the laser light. The Raman spectrumobtained is examined for the intensity I_(A) of a peak P_(A) around1,580 cm⁻¹ and the intensity I_(B) of a peak PB around 1,360 cm⁻¹. Theratio between these intensities R (R=I_(B)/I_(A)) is calculated. TheRaman R value calculated through this examination is defined as theRaman R value of the carbonaceous material in invention 1. Furthermore,the half-value width of the peak P_(A) around 1,580 cm⁻¹ in the Ramanspectrum obtained is measured, and this value is defined as the Ramanhalf-value width of the carbonaceous material in invention 1.

Conditions for the Raman spectroscopy are as follows.

-   Wavelength of argon ion laser: 514.5 nm-   Laser power on sample: 15-25 mW-   Resolution: 10-20 cm⁻¹-   Examination range: 1,100 cm⁻¹ to 1,730 cm⁻¹-   Analysis for Raman R value and Raman half-value width: background    processing-   Smoothing: simple average; convolution, 5 points

(5) BET Specific Surface Area

The BET specific surface area of the carbonaceous material, in terms ofthe value of specific surface area as determined by the BET method, isgenerally 0.1 m²·g⁻¹ or larger, preferably 0.7 m²·g⁻¹ or larger, morepreferably 1.0 m²·g⁻¹ or larger, especially preferably 1.5 m²·g⁻¹ orlarger, and is generally 100 m²·g⁻¹ or smaller, preferably 25 m²·g⁻¹ orsmaller, more preferably 15 m²·g⁻¹ or smaller, especially preferably 10m²·g⁻¹ or smaller.

When the BET specific surface area thereof is smaller than the lowerlimit of that range, use of this carbonaceous material as anegative-electrode material is apt to result in poor lithium acceptanceduring charge and in lithium deposition on the electrode surface.Consequently, there is the possibility of resulting in reducedstability. On the other hand, when the specific surface area thereofexceeds the upper limit of that range, there are cases where use of thiscarbonaceous material as a negative-electrode material is apt to resultin enhanced reactivity with the nonaqueous electrolyte and enhanced gasevolution and a preferred battery is difficult to obtain.

The determination of specific surface area by the BET method is madewith a surface area meter (a fully automatic surface area measuringapparatus manufactured by Ohukura Riken Co., Ltd.) by preliminarilydrying a sample at 350° C. for 15 minutes in a nitrogen stream and thenmeasuring the specific surface area thereof by the gas-flowing nitrogenadsorption BET one-point method using a nitrogen/helium mixture gasprecisely regulated so as to have a nitrogen pressure of 0.3 relative toatmospheric pressure. The specific surface area determined through thismeasurement is defined as the BET specific surface area of thecarbonaceous material in invention 1.

(6) Pore Diameter Distribution

The pore diameter distribution of the carbonaceous material iscalculated through a measurement of the amount of mercury intruded. Itis desirable that the carbonaceous material should have a pore diameterdistribution in which the amount of interstices which correspond topores having a diameter of from 0.01 μm to 1 μm and which include poreswithin the particles, particle surface irregularities formed by steps,and pores attributable to contact surfaces among the particles, asdetermined by mercury porosimetry (mercury intrusion method), isgenerally 0.01 cm³·g⁻¹ or larger, preferably 0.05 cm³·g⁻¹ or larger,more preferably 0.1 cm³·g⁻¹ or larger, and is generally 0.6 cm³·g⁻¹ orsmaller, preferably 0.4 cm³·g⁻¹ or smaller, more preferably 0.3 cm³·g⁻¹or smaller.

When the pore diameter distribution thereof is larger than the upperlimit of that range, there are cases where a large amount of a binder isnecessary in electrode plate formation. When the amount of intersticesthereof is smaller than the lower limit of that range, there are caseswhere high-current-density charge/discharge characteristics decrease andthe effect of diminishing electrode expansion/contraction duringcharge/discharge is not obtained.

The total volume of pores thereof corresponding to the pore diameterrange of from 0.01 μm to 100 μm, as determined by mercury porosimetry(mercury intrusion method), is generally 0.1 cm³·g⁻¹ or larger,preferably 0.25 cm³·g⁻¹ or larger, more preferably 0.4 cm³·g⁻¹ orlarger, and is generally 10 cm³·g⁻¹ or smaller, preferably 5 cm³·g⁻¹ orsmaller, more preferably 2 cm³·g⁻¹ or smaller. When the total porevolume thereof exceeds the upper limit of that range, there are caseswhere a large amount of a binder is necessary in electrode plateformation. When the total pore volume thereof is smaller than the lowerlimit of that range, there are cases where the dispersing effect of athickener or binder in electrode plate formation is not obtained.

The average pore diameter thereof is generally 0.05 μm or larger,preferably 0.1 μm or larger, more preferably 0.5 μm or larger, and isgenerally 50 μm or smaller, preferably 20 μm or smaller, more preferably10 μm or smaller. When the average pore diameter thereof exceeds theupper limit of that range, there are cases where a large amount of abinder is necessary. When the average pore diameter thereof is smallerthan the lower limit of that range, there are cases wherehigh-current-density charge/discharge characteristics decrease.

The amount of mercury intruded is measured with a mercury porosimeter(Autopore 9520, manufactured by Micromeritics Corp.) as an apparatus forthe mercury porosimetry. A sample is pretreated by placing about 0.2 gof the sample in a powder cell, closing the cell, and degassing thesample at room temperature under vacuum (50 μmHg or lower) for 10minutes. Subsequently, the pressure in the cell is reduced to 4 psia(about 28 kPa) and mercury is introduced thereinto. The internalpressure is stepwise elevated from 4 psia (about 28 kPa) to 40,000 psia(about 280 MPa) and then lowered to 25 psia (about 170 kPa). The numberof steps in the pressure elevation is 80 or larger. In each step, theamount of mercury intruded is measured after an equilibrium time of 10seconds.

A pore diameter distribution is calculated from the mercury intrusioncurve thus obtained, using the Washburn equation. Incidentally, thesurface tension (γ) and contact angle (ψ) of mercury are taken as 485dyne·cm⁻¹ (1 dyne=10 μN) and 140°, respectively. The average porediameter used is the pore diameter corresponding to a cumulative porevolume of 50%.

(7) Roundness

When the carbonaceous material is examined for roundness as an index tothe degree of sphericity thereof, the roundness thereof is preferablywithin the range shown below. Roundness is defined by “Roundness=(lengthof periphery of equivalent circle having the same area as projectedparticle shape)/(actual length of periphery of projected particleshape)”. When a particle has a roundness of 1, this particletheoretically is a true sphere.

The closer to 1 the roundness of carbonaceous-material particles havinga particle diameter in the range of 3-40 μm, the more the particles aredesirable. The roundness of the particles is desirably 0.1 or higher,preferably 0.5 or higher, more preferably 0.8 or higher, even morepreferably 0.85 or higher, especially preferably 0.9 or higher.

The higher the roundness, the more the high-current-densitycharge/discharge characteristics are improved. Consequently, when theroundness of the carbonaceous-material particles is lower than the lowerlimit of that range, there are cases where the negative-electrode activematerial has reduced suitability for loading and interparticleresistance is increased, resulting in reduced short-timehigh-current-density charge/discharge characteristics.

Roundness is determined with a flow type particle image analyzer (FPIA,manufactured by Sysmex Industrial Corp.). About 0.2 g of a sample isdispersed in a 0.2% by mass aqueous solution (about 50 mL) ofpoly(oxyethylene(20)) sorbitan monolaurate as a surfactant, and anultrasonic wave of 28 kHz is propagated to the dispersion for 1 minuteat an output of 60 W. Thereafter, particles having a particle diameterin the range of 3-40 μm are examined with the analyzer having adetection range set at 0.6-400 μm. The roundness determined through thismeasurement is defined as the roundness of the carbonaceous material ininvention 1.

Methods for improving roundness are not particularly limited. However, acarbonaceous material in which the particles have been rounded by arounding treatment is preferred because it gives an electrode in whichthe interstices among particles are uniform in shape. Examples of therounding treatment include: a method in which a shear force orcompressive force is applied to thereby mechanically make the shape ofthe particles close to sphere; and a method of mechanical/physicaltreatment in which fine particles are aggregated into particles by meansof the bonding force of a binder or of the fine particles themselves.

(8) True Density

The true density of the carbonaceous material is generally 1.4 g·cm⁻³ orhigher, preferably 1.6 g·cm⁻³ or higher, more preferably 1.8 g·cm⁻³ orhigher, especially preferably 2.0 g·cm⁻³ or higher, and is generally2.26 g·cm⁻³ or lower. When the true density of the carbonaceous materialis lower than the lower limit of that range, there are cases where thiscarbon has too low crystallinity, resulting in an increase in initialirreversible capacity. Incidentally, the upper limit of that range is atheoretical value of the true density of graphites.

The true density of the carbonaceous material is determined by theliquid-phase displacement method (pycnometer method) using butanol. Thevalue determined through this measurement is defined as the true densityof the carbonaceous material in invention 1.

(9) Tap Density

The tap density of the carbonaceous material is generally 0.1 g·cm⁻³ orhigher, preferably 0.5 g·cm⁻³ or higher, more preferably 0.7 g·cm⁻³ orhigher, especially preferably 1 g·cm⁻³ or higher, and is preferably 2g·cm⁻³ or lower, more preferably 1.8 g·cm⁻³ or lower, especiallypreferably 1.6 g·cm⁻³ or lower.

When the tap density thereof is lower than the lower limit of thatrange, there are cases where this carbonaceous material, when used in anegative electrode, is less apt to have a high loading density andcannot give a battery having a high capacity. On the other hand, whenthe tap density thereof exceeds the upper limit of that range, theamount of interparticle interstices in the electrode is too small and itis difficult to secure electrical conductivity among the particles.There are hence cases where preferred battery performances are difficultto obtain.

Tap density is determined by dropping a sample through a sieve having anopening size of 300 μm into a 20-cm³ tapping cell to fill the cell withthe sample up to the brim, subsequently conducting tapping operations1,000 times over a stroke length of 10 mm using a powder densimeter(e.g., Tap Denser, manufactured by Seishin Enterprise Co., Ltd.), andcalculating the tap density from the resultant volume of the sample andthe weight thereof. The tap density calculated through this measurementis defined as the tap density of the carbonaceous material in invention1.

(10) Orientation Ratio

The orientation ratio of the carbonaceous material is generally 0.005 orhigher, preferably 0.01 or higher, more preferably 0.015 or higher, andis generally 0.67 or lower. When the orientation ratio thereof is lowerthan the lower limit of that range, there are cases where high-densitycharge/discharge characteristics decrease. The upper limit of that rangeis a theoretical upper limit of the orientation ratio of carbonaceousmaterials.

Orientation ratio is determined by X-ray diffractometry after a sampleis molded by compaction. A molding obtained by packing 0.47 g of asample into a molding machine having a diameter of 17 mm and compactingthe sample at 58.8 MN·m⁻² is set with clay on a sample holder forexamination so as to be flush with the holder. This sample molding isexamined for X-ray diffraction. From the intensities of the resultant(110) diffraction peak and (004) diffraction peak for the carbon, theratio represented by (110) diffraction peak intensity/(004) diffractionpeak intensity is calculated. The orientation ratio calculated throughthis measurement is defined as the orientation ratio of the carbonaceousmaterial in invention 1.

Conditions for the X-ray diffractometry are as follows. Incidentally,“20” represents diffraction angle.

-   Target: Cu(Kα line) graphite monochromator-   Slit:

Divergence slit=0.5 degrees

Receiving slit=0.15 mm

Scattering slit=0.5 degrees

-   Examination range and step angle/measuring time:

(110) plane: 75°≦2θ≦80° 1°/60 sec

(004) plane: 52°≦2θ≦57° 1°/60 sec

(11) Aspect Ratio (Powder)

The aspect ratio of the carbonaceous material is generally 1 or higher,and is generally 10 or lower, preferably 8 or lower, more preferably 5or lower. When the aspect ratio thereof exceeds the upper limit of thatrange, there are cases where this carbonaceous material causes streaklines in electrode plate formation and an even coating surface cannot beobtained, resulting in a decrease in high-current-densitycharge/discharge characteristics. Incidentally, the lower limit of thatrange is a theoretical lower limit of the aspect ratio of carbonaceousmaterials.

In determining aspect ratio, particles of the carbonaceous material areexamined with a scanning electron microscope with enlargement. Fifty arearbitrarily selected from graphite particles fixed to an edge face of ametal having a thickness of 50 μm or smaller, and each particle isexamined in a three-dimensional manner while rotating or inclining thestage to which the sample is fixed. In this examination, the length ofthe longest axis A of each carbonaceous-material particle and the lengthof the shortest axis B perpendicular to that axis are measured, and theaverage of the A/B values is determined. The aspect ratio (A/B)determined through this measurement is defined as the aspect ratio ofthe carbonaceous material in invention 1.

(12) Minor-Material Mixing

Minor-material mixing means that the negative electrode and/or thenegative-electrode active material contains two or more carbonaceousmaterials differing in property. The term property herein means one ormore properties selected from the group consisting of X-ray diffractionparameter, median diameter, aspect ratio, BET specific surface area,orientation ratio, Raman R value, tap density, true density, poredistribution, roundness, and ash content.

Especially preferred examples of the minor-material mixing include: onein which the volume-based particle size distribution is not symmetricalabout the median diameter; one in which two or more carbonaceousmaterials differing in Raman R value are contained; and one in whichcarbonaceous materials differing in X-ray parameter are contained.

One example of the effects of the minor-material mixing is that theincorporation of a carbonaceous material, such as a graphite, e.g., anatural graphite or artificial graphite, or an amorphous carbon, e.g., acarbon black such as acetylene black or needle coke, as a conductivematerial serves to reduce electrical resistance.

In the case where conductive materials are incorporated asminor-material mixing, one conductive material may be incorporated aloneor any desired combination of two or more conductive materials in anydesired proportion may be incorporated. The proportion of the conductivematerial(s) to be incorporated is generally 0. 1% by mass or higher,preferably 0.5% by mass or higher, more preferably 0.6% by mass orhigher, and is generally 45% by mass or lower, preferably 40% by mass orlower, based on the carbonaceous material. When the proportion thereofis lower than the lower limit of that range, there are cases where theeffect of improving conductivity is difficult to obtain. Proportionsthereof exceeding the upper limit of that range may lead to an increasein initial irreversible capacity.

(13) Electrode Production

Any known method can be used for electrode production unless thisconsiderably lessens the effects of invention 1. For example, a binderand a solvent are added to a negative-electrode active materialoptionally together with a thickener, conductive material, filler, etc.to obtain a slurry and this slurry is applied to a current collector anddried. Thereafter, the coated current collector is pressed, whereby anelectrode can be formed.

The thickness of the negative-electrode active-material layer per oneside in the stage just before the step of injecting a nonaqueouselectrolyte in battery fabrication is generally 15 μm or larger,preferably 20 μm or larger, more preferably 30 μm or larger, and isgenerally 150 μm or smaller, preferably 120 μm or smaller, morepreferably 100 μm or smaller. The reasons for this are as follows. Whenthe thickness of the negative-electrode active-material layer is largerthan the upper limit of that range, a nonaqueous electrolyte is less aptto infiltrate into around the interface of the current collector and,hence, there are cases where high-current-density charge/dischargecharacteristics decrease. When the thickness thereof is smaller than thelower limit of that range, the proportion by volume of the currentcollector to the negative-electrode active material increases and thereare cases where battery capacity decreases. The negative-electrodeactive material may be roller-pressed to obtain a sheet electrode, ormay be subjected to compression molding to obtain a pellet electrode.

(14) Current Collector

As the current collector for holding the negative-electrode activematerial, a known one can be used at will. Examples of the currentcollector for the negative electrode include metallic materials such ascopper, nickel, stainless steel, and nickel-plated steel. Copper isespecially preferred from the standpoints of processability and cost.

In the case where the current collector is a metallic material, examplesof the shape of the current collector include metal foils, metalcylinders, metal coils, metal plates, thin metal films, expanded metals,punching metals, and metal foams. Preferred of these are thin metalfilms. More preferred are copper foils. Even more preferred are a rolledcopper foil, which is produced by the rolling process, and anelectrolytic copper foil, which is produced by the electrolytic process.Either of these can be used as a current collector.

In the case of a copper foil having a thickness smaller than 25 μm, usecan be made of a copper alloy (e.g., phosphor bronze, titanium-copper,Corson alloy, or Cu—Cr—Zr alloy) having a higher strength than purecopper.

The current collector constituted of a copper foil produced by therolling process is less apt to crack even when the negative electrode isrolled tightly or rolled at an acute angle, because the copper crystalsare oriented in the rolling direction. This current collector can beadvantageously used in small cylindrical batteries.

The electrolytic copper foil is obtained by immersing a metallic drum ina nonaqueous electrolyte containing copper ions dissolved therein,causing current to flow through the system while rotating the drum tothereby deposit copper on the drum surface, and peeling the copperdeposit from the drum. Copper may be deposited on a surface of therolled copper foil by the electrolytic process. One or each side of sucha copper foil may have undergone a surface-roughening treatment or asurface treatment (e.g., a chromate treatment in a thickness of fromseveral nanometers to about 1 μm or a priming treatment with titanium).

The current collector base is desired to further have the followingproperties.

(14-1) Average Surface Roughness (Ra)

The average surface roughness (Ra) of that side of the current collectorbase on which a thin negative-electrode active-material film is to beformed, as determined by the method provided for in JIS B 0601-1994, isnot particularly limited. However, the average surface roughness thereofis generally 0.05 μm or higher, preferably 0.1 μm or higher, morepreferably 0.15 μm or higher, and is generally 1.5 μm or lower,preferably 1.3 μm or lower, more preferably 1.0 μm or lower. This isbecause when the average surface roughness (Ra) of the current collectorbase is within that range, satisfactory charge/discharge cycleperformances can be expected. In addition, the area of the interfacebetween the base and a thin negative-electrode active-material film isincreased and adhesion to the thin negative-electrode active-materialfilm is improved. The upper limit of the average surface roughness (Ra)thereof is not particularly limited. However, a current collector basehaving an Ra of 1.5 μm or lower is usually employed because a foilhaving a practical thickness for batteries and having an average surfaceroughness (Ra) exceeding 1.5 μm is generally difficult to procure.

(14-2) Tensile Strength

Tensile strength is a quotient obtained by dividing the maximum tensileforce required before test piece breakage by the sectional area of thetest piece. In invention 1, the tensile strength is determined through ameasurement conducted with the same apparatus and by the same method asthose described in JIS Z 2241 (Method of Metallic-Material TensileTest).

The tensile strength of the current collector base is not particularlylimited. However, it is generally 100 N·mm⁻² or higher, preferably 250N·mm⁻² or higher, more preferably 400 N·mm⁻² or higher, especiallypreferably 500 N·mm⁻² or higher. The higher the tensile strength, themore the current collector base is preferred. However, the tensilestrength thereof is generally 1,000 N·mm⁻² or lower from the standpointof industrial availability. A current collector base having a hightensile strength can be inhibited from cracking with theexpansion/contraction of the thin negative-electrode active-materialfilm which occur upon charge/discharge. With this current collectorbase, satisfactory cycle performances can be obtained.

(14-3) 0.2% Proof Stress

The term 0.2% proof stress means the degree of load necessary forimparting a plastic (permanent) deformation of 0.2%. Namely, it meansthat application of that degree of load and subsequent removal thereofresult in a 0.2% deformation. The 0.2% proof stress is determinedthrough a measurement conducted with the same apparatus and by the samemethod as for tensile strength.

The 0.2% proof stress of the current collector base is not particularlylimited. However, it is desirable that the 0.2% proof stress thereofshould be generally 30 N·mm⁻² or higher, preferably 150 N·mm⁻² orhigher, especially preferably 300 N/mm² or higher. The higher the 0.2%proof stress, the more the current collector base is preferred. However,the 0.2% proof stress thereof is generally desirably 900 N·mm⁻² or lowerfrom the standpoint of industrial availability. A current collector basehaving a high 0.2% proof stress can be inhibited from plasticallydeforming with the expansion/contraction of the thin negative-electrodeactive-material film which occur upon charge/discharge. With thiscurrent collector base, satisfactory cycle performances can be obtained.

(14-4) Thickness of Current Collector

The current collector may have any desired thickness. However, thethickness thereof is generally 1 μm or larger, preferably 3 μm orlarger, more preferably 5 μm or larger, and is generally 1 mm orsmaller, preferably 100 μm or smaller, more preferably 50 μm or smaller.In case where the metal film is thinner than 1 μm, this currentcollector has reduced strength and there are hence cases where coatingis difficult. When the current collector is thicker than 100 μm, thereare cases where this collector deforms an electrode shape, e.g., arolled form. The current collector may be in a mesh form.

(15) Thickness Ratio between Current Collector and Negative-ElectrodeActive-Material Layer

The thickness ratio between the current collector and thenegative-electrode active-material layer is not particularly limited.However, the value of “(thickness of the negative-electrodeactive-material layer on one side just before impregnation with thenonaqueous electrolyte)/(thickness of the current collector)” ispreferably 150 or smaller, more preferably 20 or smaller, especiallypreferably 10 or smaller, and is preferably 0.1 or larger, morepreferably 0.4 or larger, especially preferably 1 or larger.

When the thickness ratio between the current collector and thenegative-electrode active-material layer exceeds the upper limit of thatrange, there are cases where this current collector heats up due toJoule's heat during high-current-density charge/discharge. When thatratio decreases beyond the lower limit of that range, the proportion byvolume of the current collector to the negative-electrode activematerial increases and this may reduce the capacity of the battery.

(16) Electrode Density

When the negative-electrode active material is used to form anelectrode, the electrode structure is not particularly limited. However,the density of the negative-electrode active material present on thecurrent collector is preferably g·cm⁻³ or higher, more preferably 1.2g·cm⁻³ or higher, especially preferably 1.3 g·cm⁻³ or higher, and ispreferably 2 g·cm⁻³ or lower, more preferably 1.9 g·cm⁻³ or lower, evenmore preferably 1.8 g·cm⁻³ or lower, especially preferably 1.7 g·cm⁻³ orlower. When the density of the negative-electrode active materialpresent on the current collector exceeds the upper limit of that range,there are cases where the negative-electrode active-material particlesare broken and this increases the initial irreversible capacity andreduces the infiltration of a nonaqueous electrolyte into around thecurrent collector/negative-electrode active material interface. As aresult, high-current-density charge/discharge characteristics maydecrease. When the density thereof is lower than the lower limit of thatrange, there are cases where electrical conductivity among thenegative-electrode active-material particles decreases and thisincreases battery resistance, resulting in a reduced capacity per unitvolume.

(17) Binder

The binder for binding the negative-electrode active material is notparticularly limited so long as it is stable to the nonaqueouselectrolyte and to the solvent to be used for electrode production.

Examples thereof include resinous polymers such as polyethylene,polypropylene, poly(ethylene terephthalate), poly(methyl methacrylate),aromatic polyamides, cellulose, and nitrocellulose; rubbery polymerssuch as SBR (styrene/butadiene rubbers), isoprene rubbers, butadienerubbers, fluororubbers, NBR (acrylonitrile/butadiene rubbers), andethylene/propylene rubbers; styrene/butadiene/styrene block copolymersor products of hydrogenation thereof; thermoplastic elastomeric polymerssuch as EPDM (ethylene/propylene/diene terpolymers),styrene/ethylene/butadiene/styrene copolymers, andstyrene/isoprene/styrene block copolymers or products of hydrogenationthereof; flexible resinous polymers such as syndiotactic1,2-polybutadiene, poly(vinyl acetate), ethylene/vinyl acetatecopolymers, and propylene/α-olefin copolymers; fluorochemical polymerssuch as poly(vinylidene fluoride), polytetrafluoroethylene, fluorinatedpoly(vinylidene fluoride), and polytetrafluoroethylene/ethylenecopolymers; and polymer compositions having the property of conductingalkali metal ions (especially lithium ions). One of these maybe usedalone, or any desired combination of two or more thereof in any desiredproportion may be used.

The kind of the solvent to be used for forming a slurry is notparticularly limited so long as it is a solvent in which thenegative-electrode active material and binder and the thickener andconductive material which are optionally used according to need can bedissolved or dispersed. Either an aqueous solvent or an organic solventmay be used.

Examples of the aqueous solvent include water and alcohols. Examples ofthe organic solvent include N-methylpyrrolidone (NMP),dimethylformamide, dimethylacetamide, methyl ethyl ketone,cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine,N,N-dimethylaminopropylamine, tetrahydrofuran (THF), toluene, acetone,diethyl ether, hexamethylphosphoramide, dimethyl sulfoxide, benzene,xylene, quinoline, pyridine, methylnaphthalene, and hexane.

Especially when an aqueous solvent is used, it is preferred to add adispersant or the like in combination with a thickener and prepare aslurry using a latex of, e.g., SBR. One of those solvents may be usedalone, or any desired combination of two or more thereof in any desiredproportion may be used.

The proportion of the binder to the negative-electrode active materialis preferably 0.1% by mass or higher, more preferably 0.5% by mass orhigher, especially preferably 0.6% by mass or higher, and is preferably20% by mass or lower, more preferably 15% by mass or lower, even morepreferably 10% by mass or lower, especially preferably 8% by mass orlower. In case where the proportion of the binder to thenegative-electrode active material exceeds the upper limit of thatrange, the proportion of the binder which does not contribute to batterycapacity increases and this may lead to a decrease in battery capacity.When the binder amount is smaller than the lower limit of that range,there are cases where the negative electrode has a reduced strength.

Especially when the binder includes a rubbery polymer represented by SBRas the main component, the proportion of this binder to thenegative-electrode active material is generally 0.1% by mass or higher,preferably 0.5% by mass or higher, more preferably 0.6% by mass orhigher, and is generally 5% by mass or lower, preferably 3% by mass orlower, more preferably 2% by mass or lower.

In the case where the binder includes a fluorochemical polymerrepresented by poly(vinylidene fluoride) as the main component, theproportion of this binder to the negative-electrode active material isgenerally 1% by mass or higher, preferably 2% by mass or higher, morepreferably 3% by mass or higher, and is generally 15% by mass or lower,preferably 10% by mass or lower, more preferably 8% by mass or lower.

A thickener is used generally for the purpose of regulating the slurryviscosity. The thickener is not particularly limited. Examples thereofinclude carboxymethyl cellulose, methyl cellulose, hydroxymethylcellulose, ethyl cellulose, poly(vinyl alcohol), oxidized starch,phosphorylated starch, casein, and salts of these. One of thesethickeners maybe used alone, or any desired combination of two or morethereof in any desired proportion may be used.

In the case where such a thickener is further added, the proportion ofthe thickener to the negative-electrode active material is generally0.1% by mass or higher, preferably 0.5% by mass or higher, morepreferably 0.6% by mass or higher, and is generally 5% by mass or lower,preferably 3% by mass or lower, more preferably 2% by mass or lower.When the proportion of the thickener to the negative-electrode activematerial is lower than the lower limit of that range, there are caseswhere applicability decreases considerably. Proportions thereofexceeding the upper limit of that range result in a reduced proportionof the negative-electrode active material in the negative-electrodeactive-material layer, and this may pose a problem that battery capacitydecreases and a problem that resistance among the particles of thenegative-electrode active material increases.

(18) Orientation Ratio in Electrode Plate

The orientation ratio in the electrode plate is generally 0.001 orhigher, preferably 0.005 or higher, more preferably 0.01 or higher, andis generally 0.67 or lower. When the orientation ratio therein is lowerthan the lower limit of that range, there are cases where high-densitycharge/discharge characteristics decrease. The upper limit of that rangeis a theoretical upper limit of orientation ratio incarbonaceous-material electrodes.

An examination for determining the orientation ratio in the electrodeplate is as follows. The negative electrode which has been pressed to atarget density is examined by X-ray diffractometry to determine theorientation ratio of the negative-electrode active material in thiselectrode. Although specific techniques therefor are not particularlylimited, a standard method is as follows. The peaks attributable to the(110) diffraction and (004) diffraction of the carbon obtained by X-raydiffractometry are subjected to peak separation by fitting withasymmetric Pearson VII as a profile function. Thus, the integratedintensities of the (110) diffraction and (004) diffraction peaks arecalculated. From the integrated intensities obtained, the ratiorepresented by (integrated intensity of (110) diffraction)/(integratedintensity of (004) diffraction) is calculated. The negative-electrodeactive-material orientation ratio for the electrode thus calculated isdefined as the orientation ratio in the electrode plate employing thecarbonaceous material in invention 1.

Conditions for this X-ray diffractometry are as follows. Incidentally,“20” represents diffraction angle.

-   Target: Cu(Kα line) graphite monochromator-   Slit:

Divergence slit=1 degree

Receiving slit=0.1 mm

Scattering slit=1 degree

-   Examination range and step angle/measuring time:

(110) plane: 76.5°≦2θ≦78.5° 0.01°/3 sec

(004) plane: 53.5°≦2θ≦56.0° 0.01°/3 sec

-   Sample preparation:

The electrode is fixed to a glass plate with a double-facedpressure-sensitive adhesive tape having a thickness of 0.1 mm.

<2-3-3. Metal Compound Material, Constitution and Properties of NegativeElectrode Employing Metal Compound Material, and Method of Preparationthereof>

The metal compound material to be used as a negative-electrode activematerial is not particularly limited so long as the material is capableof occluding/releasing lithium. Use may be made of an elemental metal oralloy which forms a lithium alloy or any of compounds thereof, such asoxides, carbides, nitrides, silicides, sulfides, and phosphides.Examples of such metal compounds include compounds containing a metalsuch as Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, orZn. In particular, the negative-electrode active material preferably isan elemental metal or alloy which forms a lithium alloy. It is preferredthat the active material should be a material containing any of themetals and semimetals in Group 13 and Group 14 (i.e., carbon isexcluded). Furthermore, it is preferred that the active material shouldbe an elemental metal which is silicon (Si), tin (Sn), or lead (Pb)(hereinafter, these three elements are often referred to as “specificmetallic elements”) or an alloy containing atoms of any of these metalsor a compound of one or more of these metals (specific metallicelements). One of such materials may be used alone, or any desiredcombination of two or more of these in any desired proportion may beused.

Examples of the negative-electrode active material including atoms of atleast one member selected from the specific metallic elements include:the elemental metal which is any one of the specific metallic elements;alloys constituted of two or more specific metal elements; alloysconstituted of one or more specific metal elements and one or moremetallic elements of another kind; compounds containing one or morespecific metallic elements; and composite compounds, e.g., oxides,carbides, nitrides, silicides, sulfides, or phosphides, of thesecompounds. By using any of these elemental metals, alloys, and metalcompounds as a negative-electrode active material, a battery having ahigher capacity can be obtained.

Examples of the negative-electrode active material further includecompounds formed by the complicated bonding of any of those compositecompounds to one or more elemental metals or alloys or to severalelements, e.g., nonmetallic elements. More specifically, in the case ofsilicon and tin, for example, use can be made of an alloy of thoseelements with a metal which does not function as a negative electrode.In the case of tin, for example, use may be made of a complicatedcompound constituted of a combination of five to six elements includingtin, a metal which functions as a negative electrode and is not silicon,a metal which does not function as a negative electrode, and anonmetallic element.

Preferred of those negative-electrode active materials are the elementalmetal which is any one of the specific metallic elements, alloys of twoor more of the specific metallic elements, and oxides, carbides,nitrides, and other compounds of the specific metallic elements. This isbecause these negative-electrode active materials give a battery havinga high capacity per unit weight. Especially preferred are the elementalmetal (s), alloys, oxides, carbides, nitrides, and the like of siliconand/or tin from the standpoints of capacity per unit weight andenvironmental burden.

The following compounds containing silicon and/or tin also are preferredbecause these compounds bring about excellent cycle performances,although inferior in capacity per unit weight to the elemental metals oralloys thereof.

-   A “silicon and/or tin oxide” in which the elemental ratio of the    silicon and/or tin to the oxygen is generally 0.5 or higher,    preferably 0.7 or higher, more preferably 0.9 or higher, and is    generally 1.5 or lower, preferably 1.3 or lower, more preferably 1.1    or lower.-   A “silicon and/or tin nitride” in which the elemental ratio of the    silicon and/or tin to the nitrogen is generally 0.5 or higher,    preferably 0.7 or higher, more preferably 0.9 or higher, and is    generally 1.5 or lower, preferably 1.3 or lower, more preferably 1.1    or lower.-   A “silicon and/or tin carbide” in which the elemental ratio of the    silicon and/or tin to the carbon is generally 0.5 or higher,    preferably 0.7 or higher, more preferably 0.9 or higher, and is    generally 1.5 or lower, preferably 1.3 or lower, more preferably 1.1    or lower.

Any one of the negative-electrode active materials described above maybe used alone, or any desired combination of two or more thereof in anydesired proportion may be used.

The negative electrode in the nonaqueous-electrolyte secondary batteryof invention 1 can be produced by any known method. Examples of methodsfor negative-electrode production include: a method in which a binder, aconductive material, and other ingredients are added to any of thenegative-electrode active materials described above and this mixture isdirectly roller-pressed to form a sheet electrode; and a method in whichthe mixture is compression-molded to form a pellet electrode. Usually,however, use is made of a method in which a thin film layer containingany of the negative-electrode active materials described above(negative-electrode active-material layer) is formed on a currentcollector for negative electrodes (hereinafter sometimes referred to as“negative-electrode current collector”) by a technique such as, e.g.,coating fluid application, vapor deposition, sputtering, or plating. Inthis case, a negative-electrode active-material layer may be formed on anegative-electrode current collector by adding a binder, thickener,conductive material, solvent, etc. to the negative-electrode activematerial to obtain a mixture in a slurry form, applying this mixture tothe negative-electrode current collector, drying the mixture applied,and then pressing the coated current collector to densify the coating.

Examples of the material of the negative-electrode current collectorinclude copper, copper alloys, nickel, nickel alloys, and stainlesssteel. Copper foils are preferred of these materials from thestandpoints of processability into thin films and cost.

The thickness of the negative-electrode current collector is generally 1μm or larger, preferably 5 μm or larger, and is generally 100 μm orsmaller, preferably 50 μm or smaller. The reasons for this are asfollows. In case where the negative-electrode current collector is toothick, this may result in too large a decrease in the capacity of thewhole battery. Conversely, in case where the current collector is toothin, this collector may be difficult to handle.

It is preferred that the surface of each of those negative-electrodecurrent collectors should be subjected to a surface-roughening treatmentbeforehand in order to improve the effect of binding thenegative-electrode active-material layer to be formed on the surface.Examples of techniques for the surface roughening include blasting,rolling with a roll having a roughened surface, and mechanical polishingin which the collector surface is polished with an abrasive cloth orpaper having abrasive particles fixed thereto, a grindstone, an emerywheel, a wire brush equipped with steel bristles, or the like. Examplesthereof further include electrolytic polishing and chemical polishing.

It is also possible to use a negative-electrode current collector of theperforated type, such as an expanded metal or a punching metal, as anegative-electrode current collector having a reduced weight in order toimprove energy density per unit weight of the battery. Anegative-electrode current collector of this type can be varied inweight at will by changing the percentage of openings thereof.Furthermore, in the case where a negative-electrode active-materiallayer is formed on each side of a negative-electrode current collectorof this type, the negative-electrode active-material layers are evenless apt to peel off because of the effect of rivetting through theholes. It should, however, be noted that too high a percentage ofopenings results in a reduced contact area between eachnegative-electrode active-material layer and the negative-electrodecurrent collector and hence in reduced, rather than increased adhesionstrength.

The slurry for forming a negative-electrode active-material layer isgenerally produced by adding a binder, a thickener, etc. to anegative-electrode material. The term “negative-electrode material” inthis description means a material including both a negative-electrodeactive material and a conductive material.

It is preferred that the content of the negative-electrode activematerial in the negative-electrode material should be generally 70% bymass or higher, especially 75% by mass or higher, and be generally 97%by mass or lower, especially 95% by mass or lower. The reasons for thisare as follows. In case where the content of the negative-electrodeactive material is too low, a secondary battery employing the resultantnegative electrode tends to have an insufficient capacity. In case wherethe content thereof is too high, the relative content of the binder andother components is insufficient and this tends to result ininsufficient strength of the negative electrode obtained. When two ormore negative-electrode active materials are used in combination, thiscombination may be used so that the total amount of thenegative-electrode active materials satisfies that range.

Examples of the conductive material for use in the negative electrodeinclude metallic materials such as copper and nickel, and carbonmaterials such as graphites and carbon blacks. One of these materialsmaybe used alone, or any desired combination of two or more thereof inany desired proportion may be used. In particular, use of a carbonmaterial as the conductive material is preferred because the carbonmaterial functions also as an active material. It is preferred that thecontent of the conductive material in the negative electrode should begenerally 3% by mass or higher, especially 5% by mass or higher, and begenerally 30% by mass or lower, especially 25% by mass or lower. Thereasons for this are as follows. In case where the content of theconductive material is too low, conductivity tends to be insufficient.In case where the content thereof is too high, the relative content ofthe negative-electrode active material and other components isinsufficient and this tends to result in decreases in battery capacityand strength. When two or more conductive materials are used incombination, this combination may be used so that the total amount ofthe conductive materials satisfies that range.

As the binder for the negative electrode, any desired binder can be usedso long as it is safe for the solvent to be used in electrode productionand for the electrolyte. Examples thereof include poly(vinylidenefluoride), polytetrafluoroethylene, polyethylene, polypropylene,styrene/butadiene rubbers, isoprene rubbers, butadiene rubbers,ethylene/acrylic acid copolymers, and ethylene/methacrylic acidcopolymers. One of these binders may be used alone, or any desiredcombination of two or more thereof in any desired proportion maybe used.It is preferred that the content of the binder should be generally 0.5parts by weight or larger, especially 1 part by weight or larger, and begenerally 10 parts by weight or smaller, especially 8 parts by weight orsmaller, per 100 parts by weight of the negative-electrode material. Thereasons for this are as follows. In case where the content of the binderis too low, the resultant electrode tends to have insufficient strength.In case where the content thereof is too high, the relative content ofthe negative-electrode active material and other components isinsufficient and this tends to result in insufficient battery capacityand insufficient conductivity. When two or more binders are used incombination, this combination may be used so that the total amount ofthe binders satisfies that range.

Examples of the thickener for use in the negative electrode includecarboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose,ethyl cellulose, polyvinyl alcohol), oxidized starch, phosphorylatedstarch, and casein. One of these thickeners may be used alone, or anydesired combination of two or more thereof in any desired proportion maybe used. A thickener may be used according to need. In the case of usinga thickener, it is preferred to use the thickener so that the contentthereof in the negative-electrode active-material layer is in the rangeof generally from 0.5% by mass to 5% by mass.

The slurry for forming a negative-electrode active-material layer isprepared by mixing the negative-electrode active material with aconductive material, a binder, and a thickener according to need usingan aqueous solvent or an organic solvent as a dispersion medium. Wateris generally used as the aqueous solvent. However, a solvent other thanwater, such as an alcohol, e.g., ethanol, a cyclic amide, e.g.,N-methylpyrrolidone, or the like, can be used in combination with waterin a proportion of up to about 30% by mass based on the water. Examplesof the organic solvent usually include cyclic amides such asN-methylpyrrolidone, linear amides such as N,N-dimethylformamide andN,N-dimethylacetamide, aromatic hydrocarbons such as anisole, toluene,and xylene, and alcohols such as butanol and cyclohexanol. Preferred ofthese are cyclic amides such as N-methylpyrrolidone and linear amidessuch as N,N-dimethylformamide and N,N-dimethylacetamide. Any one of suchsolvents may be used alone, or any desired combination of two or morethereof in any desired proportion may be used.

The viscosity of the slurry is not particularly limited so long as theslurry is applicable to a current collector. The slurry may be suitablyprepared while changing the amount of the solvent to be used, etc. sothat the slurry is applicable.

The slurry obtained is applied to the negative-electrode currentcollector described above, and the coated collector is dried and thenpressed, whereby a negative-electrode active-material layer is formed.Techniques for the application are not particularly limited, and atechnique which itself is known can be employed. Techniques for thedrying also are not particularly limited, and use can be made of a knowntechnique such as, e.g., natural drying, drying by heating, or vacuumdrying.

The negative-electrode active material is used to produce an electrodein the manner described above. The structure of this electrode is notparticularly limited. However, the density of the active materialpresent on the current collector is preferably 1 g·cm⁻³ or higher, morepreferably 1.2 g·cm⁻³ or higher, especially preferably 1.3 g·cm⁻³ orhigher, and is preferably 2 g·cm⁻³ or lower, more preferably 1.9 g·cm⁻³or lower, even more preferably 1.8 g·cm⁻³ or lower, especiallypreferably 1.7 g·cm⁻³ or lower.

When the density of the active material present on the current collectorexceeds the upper limit of that range, there are cases where particlesof the active material are destroyed and this causes an increase ininitial irreversible capacity and reduces the infiltration of thenonaqueous electrolyte into around the current collector/active materialinterface, resulting in impaired high-current-density charge/dischargecharacteristics. When the density thereof is lower than the lower limitof that range, there are cases where conductivity between particles ofthe active material decreases, resulting in increased battery resistanceand reduced capacity per unit volume.

<2-3-4. Lithium-Containing Metal Composite Oxide Material, Constitutionand Properties of Negative Electrode Employing Lithium-Containing MetalComposite Oxide Material, and Method of Preparation thereof>

The lithium-containing metal composite oxide material to be used as anegative-electrode active material is not particularly limited so longas the material is capable of occluding/releasing lithium. However, alithium-containing composite metal oxide material containing titanium ispreferred, and a composite oxide of lithium and titanium (hereinafterabbreviated to “lithium-titanium composite oxide”) is especiallypreferred. Namely, use of a lithium-titanium composite oxide having aspinel structure is especially preferred because incorporation of thiscomposite oxide into a negative-electrode active material for lithiumion secondary batteries is effective in considerably reducing outputresistance.

Also preferred are lithium-titanium composite oxides in which thelithium or titanium has been replaced by one or more other metallicelements, e.g., at least one element selected from the group consistingof Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb.

Such metal oxide preferably is a lithium-titanium composite oxiderepresented by general formula (5) wherein 0.7≦x≦1.5, 1.5≦y≦2.3, and0≦z≦1.6, because the structure thereof is stable during lithium iondoping/undoping.

Li_(x)Ti_(y)M₂O₄   (5)

[In general formula (5), M represents at least one element selected fromthe group consisting of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, andNb.]

Of the compositions represented by general formula (5), structuresrepresented by general formula (5) wherein (a) 1.2≦x≦1.4, 1.5≦y≦1.7, andz=0, (b) 0.9≦x≦1.1, 1.9≦y≦2.1, and z=0, or (c) 0.7≦x≦0.9, 2.1≦y≦2.3, andz=0 are especially preferred because they bring about a satisfactorybalance among battery performances.

Especially preferred typical compositions of those compounds are:Li_(4/3)Ti_(5/3)O₄ for (a), Li₁Ti₂O₄ for (b), and Li_(4/5)Ti_(11/5)O₄for (c). Preferred examples of the structure wherein z≠0 includeLi_(4/3)Ti_(4/3)Al_(1/3)O₄.

It is preferred that the lithium-titanium composite oxide for use as thenegative-electrode active material in invention 1 should satisfy atleast one of the following features (1) to (13) concerning properties,shape, etc., besides the requirements described above. Especiallypreferably, the composite oxide simultaneously satisfies two or more ofthe following features.

(1) BET Specific Surface Area

The BET specific surface area of the lithium-titanium composite oxidefor use as the negative-electrode active material, as determined by theBET method, is preferably 0.5 m²·g⁻¹ or larger, more preferably 0.7m²·g⁻¹ or larger, even more preferably 1.0 m²·g⁻¹ or larger, especiallypreferably 1.5 m²·g⁻¹ or larger, and is preferably 200 m²·g⁻¹ orsmaller, more preferably 100 m²·g⁻¹ or smaller, even more preferably 50m²·g⁻¹ or smaller, especially preferably 25 m²·g⁻¹ or smaller.

When the BET specific surface area thereof is smaller than the lowerlimit of that range, there are cases where use of this composite oxideas a negative-electrode material results in a reduced reaction areaavailable for contact with the nonaqueous electrolyte and in an increasein output resistance. On the other hand, in case where the BET specificsurface area thereof exceeds the upper limit of that range, theproportion of surfaces and edge faces of crystals of thetitanium-containing metal oxide increases and this causes crystaldeformation. There are hence cases where irreversible capacity becomesnot negligible and a preferred battery is difficult to obtain.

BET specific surface area is determined with a surface area meter (afully automatic surface area measuring apparatus manufactured by OhukuraRiken Co., Ltd.) by preliminarily drying a sample at 350° C. for 15minutes in a nitrogen stream and then measuring the specific surfacearea thereof by the gas-flowing nitrogen adsorption BET one-point methodusing a nitrogen/helium mixture gas precisely regulated so as to have anitrogen pressure of 0.3 relative to atmosphere pressure. The specificsurface area determined through this measurement is defined as the BETspecific surface area of the lithium-titanium composite oxide ininvention 1.

(2) Volume-Average Particle Diameter

The volume-average particle diameter (secondary-particle diameter in thecase where the primary particles have aggregated to form secondaryparticles) of the lithium-titanium composite oxide is defined as thevolume-average particle diameter (median diameter) determined by thelaser diffraction/scattering method.

The volume-average particle diameter of the lithium-titanium compositeoxide is generally 0.1 μm or larger, preferably 0.5 μm or larger, morepreferably 0.7 μm or larger, and is generally 50 μm or smaller,preferably 40 μm or smaller, even more preferably 30 μm or smaller,especially preferably 25 μm or smaller.

Volume-average particle diameter is determined by dispersing thelithium-titanium composite powder in a 0.2% by mass aqueous solution (10mL) of poly(oxyethylene (20)) sorbitan monolaurate as a surfactant andexamining the dispersion with a laser diffraction/scattering typeparticle size distribution analyzer (LA-700, manufactured by HORIBA,Ltd.). The median diameter determined by this measurement is defined asthe volume-average particle diameter of the carbonaceous material ininvention 1.

When the volume-average particle diameter of the lithium-titaniumcomposite oxide is smaller than the lower limit of that range, there arecases where a large amount of a binder is necessary in electrodeproduction and this results in a decrease in battery capacity. When thevolume-average particle diameter thereof exceeds the upper limit of thatrange, there are cases where such a composite oxide is undesirable fromthe standpoint of battery production because an uneven coating surfaceis apt to result when an electrode plate is produced.

(3) Average Primary-Particle Diameter

In the case where the primary particles have aggregated to formsecondary particles, the average primary-particle diameter of thelithium-titanium composite oxide is generally 0.01 μm or larger,preferably 0.05 μm or larger, more preferably 0.1 μm or larger,especially preferably 0.2 μm or larger, and is generally 2μm or smaller,preferably 1.6 μm or smaller, more preferably 1.3 μm or smaller,especially preferably 1 μm or smaller. In case where the volume-averageprimary-particle diameter thereof exceeds the upper limit of that range,spherical secondary particles are difficult to form and this adverselyinfluences powder loading or results in a considerably reduced specificsurface area. There may hence be a high possibility that batteryperformances such as output characteristics might decrease. When theaverage primary-particle diameter thereof is smaller than the lowerlimit of that range, crystal growth is usually insufficient and, hence,there are cases where use of this composite oxide gives a secondarybattery having reduced performances, e.g., poor charge/dischargereversibility.

Primary-particle diameter is determined through an examination with ascanning electron microscope (SEM). Specifically, arbitrarily selected50 primary-particle images in a photograph having a magnificationcapable of particle observation, e.g., 10,000-100,000 diameters, eachare examined for the length of the longest segment of a horizontal linewhich extends across the primary-particle image from one side to theother side of the boundary. These measured lengths are averaged, wherebythe average value can be determined.

(4) Shape

The shape of the particles of the lithium-titanium composite oxide maybe any of massive, polyhedral, spherical, ellipsoidal, platy, acicular,columnar, and other shapes such as those in common use. Preferred ofthese is one in which the primary particles have aggregated to formsecondary particles and these secondary particles have a spherical orellipsoidal shape.

In electrochemical elements, the active material in each electrodeusually expands/contracts with the charge/discharge of the element and,hence, deterioration is apt to occur, such as active-material breakageand conduction path breakage, due to the stress caused by theexpansion/contraction. Because of this, an active material in which theprimary particles have aggregated to form secondary particles ispreferable to an active material composed of primary particles onlysince the particles in the former active material relieve the stresscaused by expansion/contraction to prevent deterioration.

Furthermore, particles of a spherical or ellipsoidal shape arepreferable to particles showing axial orientation, e.g., platy ones,because the former particles are less apt to orient during electrodemolding and hence this electrode is reduced in expansion/contractionduring charge/discharge, and because these particles are apt to beevenly mixed with a conductive material in electrode production.

(5) Tap Density

The tap density of the lithium-titanium composite oxide is preferably0.05 g·cm⁻³ or higher, more preferably 0.1 g·cm⁻³ or higher, even morepreferably 0.2 g·cm⁻³ or higher, especially preferably 0.4 g·cm⁻³ orhigher, and is preferably 2.8 g·cm⁻³ or lower, more preferably 2.4g·cm⁻³ or lower, especially preferably 2 g·cm⁻³ or lower. In case wherethe tap density thereof is lower than the lower limit of that range,this composite oxide, when used in a negative electrode, is less apt tohave a high loading density and has a reduced interparticle contactarea. There are hence cases where interparticle resistance increases andoutput resistance increases. On the other hand, in case where the tapdensity thereof exceeds the upper limit of that range, the electrode hastoo small an amount of interparticle interstices and a reduced amount ofchannels for the nonaqueous electrolyte. There are hence cases whereoutput resistance increases.

The tap density of a sample is determined by dropping the sample througha sieve having an opening size of 300 μm into a 20-cm³ tapping cell tofill the cell with the sample up to the brim, subsequently conductingtapping operations 1,000 times over a stroke length of 10 mm using apowder densimeter (e.g., Tap Denser, manufactured by Seishin EnterpriseCo., Ltd.), and calculating a density from the resultant volume of thesample and the weight thereof. The tap density calculated through thismeasurement is defined as the tap density of the lithium-titaniumcomposite oxide in invention 1.

(6) Roundness

When the lithium-titanium composite oxide is examined for roundness asan index to the degree of sphericity thereof, the roundness thereof ispreferably within the range shown below. Roundness is defined by“Roundness=(length of periphery of equivalent circle having the samearea as projected particle shape)/(actual length of periphery ofprojected particle shape)”. When a particle has a roundness of 1, thisparticle theoretically is a true sphere.

The closer to 1 the roundness of the lithium-titanium composite oxide,the more the particles thereof are preferred. The roundness of thecomposite oxide is generally 0.10 or higher, preferably 0.80 or higher,more preferably 0.85 or higher, especially preferably 0.90 or higher.The higher the roundness, the more the high-current-densitycharge/discharge characteristics are improved. Consequently, when theroundness of the composite oxide is lower than the lower limit of thatrange, there are cases where the negative-electrode active material hasreduced suitability for loading and interparticle resistance isincreased, resulting in reduced short-time high-current-densitycharge/discharge characteristics.

Roundness is determined with a flow type particle image analyzer (FPIA,manufactured by Sysmex Industrial Corp.). About 0.2 g of a sample isdispersed in a 0.2% by mass aqueous solution (about 50 mL) ofpoly(oxyethylene(20)) sorbitan monolaurate as a surfactant, and anultrasonic wave of 28 kHz is propagated to the dispersion for 1 minuteat an output of 60 W. Thereafter, particles having a particle diameterin the range of 3-40 μm are examined with the analyzer having adetection range set at 0.6-400 μm. The roundness determined through thismeasurement is defined as the roundness of the lithium-titaniumcomposite oxide in invention 1.

(7) Aspect Ratio

The aspect ratio of the lithium-titanium composite oxide is generally 1or higher, and is generally 5 or lower, preferably 4 or lower, morepreferably 3 or lower, especially preferably 2 or lower. When the aspectratio thereof exceeds the upper limit of that range, there are caseswhere this composite oxide causes streak lines in electrode plateformation and an even coating surface cannot be obtained, resulting in adecrease in short-time high-current-density charge/dischargecharacteristics. Incidentally, the lower limit of that range is atheoretical lower limit of the aspect ratio of lithium-titaniumcomposite oxides.

In determining aspect ratio, particles of the lithium-titanium compositeoxide are examined with a scanning electron microscope with enlargement.Fifty are arbitrarily selected from composite-oxide particles fixed toan edge face of a metal having a thickness of 50 μm or smaller, and eachparticle is examined in a three-dimensional manner while rotating orinclining the stage to which the sample is fixed. In this examination,the length of the longest axis A of each particle and the length of theshortest axis B perpendicular to that axis are measured, and the averageof the A/B values is determined. The aspect ratio (A/B) determinedthrough this measurement is defined as the aspect ratio of thelithium-titanium composite oxide in invention 1.

(8) Processes for Producing Negative-Electrode Active Material

Processes for producing the lithium-titanium composite oxide are notparticularly limited unless they depart from the spirit of invention 1.Examples thereof include several processes, and processes in general usefor producing inorganic compounds may be employed.

Examples thereof include a method in which a titanium source, e.g.,titanium oxide, is evenly mixed with a lithium source, e.g., LiOH,Li₂CO₃, or LiNO₃, and optionally with a source of other element (s) andthis mixture is burned at a high temperature to obtain the activematerial.

Especially for producing spherical or ellipsoidal active materials,various techniques are usable. Examples thereof include: a method whichcomprises dissolving or pulverizing/dispersing a titanium source, e.g.,titanium oxide, optionally together with a source of other element(s) ina solvent, e.g., water, regulating the pH of the solution or dispersionwith stirring to produce a spherical precursor, recovering andoptionally drying the precursor, subsequently adding thereto a lithiumsource, e.g., LiOH, Li₂CO₃, or LiNO₃, and burning the mixture at a hightemperature to obtain the active material.

Another example is a method which comprises dissolving orpulverizing/dispersing a titanium source, e.g., titanium oxide,optionally together with a source of other element(s) in a solvent,e.g., water, drying and forming the solution or dispersion with a spraydryer or the like to obtain a spherical or ellipsoidal precursor, addingthereto a lithium source, e.g., LiOH, Li₂CO₃, or LiNO₃, and burning themixture at a high temperature to obtain the active material.

Still another example is a method which comprises dissolving orpulverizing/dispersing a titanium source, e.g., titanium oxide, togetherwith a lithium source, e.g., LiOH, Li₂CO₃, or LiNO₃, and optionally witha source of other element(s) in a solvent, e.g., water, drying andforming the solution or dispersion with a spray dryer or the like toobtain a spherical or ellipsoidal precursor, and burning the precursorat a high temperature to obtain the active material.

In those steps, one or more of elements other than Ti, such as, e.g.,Al, Mn, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, C, Si, Sn,and Ag, can be caused to be present in the titanium-containing metaloxide structure and/or present so as be in contact with thetitanium-containing oxide. The incorporation of such elements can beused to regulate the operating voltage and capacity of the battery.

(9) Electrode Production

Any known method can be used for electrode production. For example, abinder and a solvent are added to a negative-electrode active materialoptionally together with a thickener, conductive material, filler, etc.to obtain a slurry and this slurry is applied to a current collector anddried. Thereafter, the coated current collector is pressed, whereby anelectrode can be formed.

The thickness of the negative-electrode active-material layer per oneside in the stage just before the step of injecting a nonaqueouselectrolyte in battery fabrication is generally 15 μm or larger,preferably 20 μm or larger, more preferably 30 μm or larger. The upperlimit thereof desirably is 150 μm or smaller, preferably 120 μm orsmaller, more preferably 100 μm or smaller.

When the thickness thereof is larger than the upper limit of that range,a nonaqueous electrolyte is less apt to infiltrate into around theinterface of the current collector and, hence, there are cases wherehigh-current-density charge/discharge characteristics decrease. When thethickness thereof is smaller than the lower limit of that range, theproportion by volume of the current collector to the negative-electrodeactive material increases and there are cases where battery capacitydecreases. The negative-electrode active material may be roller-pressedto obtain a sheet electrode, or may be subjected to compression moldingto obtain a pellet electrode.

(10) Current Collector

As the current collector for holding the negative-electrode activematerial, a known one can be used at will. Examples of the currentcollector for the negative electrode include metallic materials such ascopper, nickel, stainless steel, and nickel-plated steel. Copper isespecially preferred of these from the standpoints of processability andcost.

In the case where the current collector is a metallic material, examplesof the shape of the current collector include metal foils, metalcylinders, metal coils, metal plates, thin metal films, expanded metals,punching metals, and metal foams. Preferred of these are metal foilfilms including copper (Cu) and/or aluminum (Al). More preferred arecopper foils and aluminum foils. Even more preferred are a rolled copperfoil, which is produced by the rolling process, and an electrolyticcopper foil, which is produced by the electrolytic process. Either ofthese can be used as a current collector.

In the case of a copper foil having a thickness smaller than 25 μm, usecan be made of a copper alloy (e.g., phosphor bronze, titanium-copper,Corson alloy, or Cu—Cr—Zr alloy) having a higher strength than purecopper. Furthermore, an aluminum foil can be advantageously used becauseit has a low specific gravity and, hence, use of the foil as a currentcollector can reduce the weight of the battery.

The current collector comprising a copper foil produced by the rollingprocess is less apt to crack even when the negative electrode is rolledtightly or rolled at an acute angle, because the copper crystals areoriented in the rolling direction. This current collector can beadvantageously used in small cylindrical batteries.

The electrolytic copper foil is obtained by immersing a metallic drum ina nonaqueous electrolyte containing copper ions dissolved therein,causing current to flow through the system while rotating the drum tothereby deposit copper on the drum surface, and peeling the copperdeposit from the drum. Copper may be deposited on a surface of therolled copper foil by the electrolytic process. One or each side of sucha copper foil may have undergone a surface-roughening treatment or asurface treatment (e.g., a chromate treatment in a thickness of fromseveral nanometers to about 1 μm or a priming treatment with titanium).

The current collector base is desired to further have the followingproperties.

(10-1) Average Surface Roughness (Ra)

The average surface roughness (Ra) of that side of the current collectorbase on which a thin active-material film is to be formed, as determinedby the method provided for in JIS B0601-1994, is not particularlylimited. However, the average surface roughness thereof is generally0.01 μm or higher, preferably 0.03 μm or higher, and is generally 1.5 μmor lower, preferably 1.3 μm or lower, more preferably 1.0 μm or lower.

This is because when the average surface roughness (Ra) of the currentcollector base is within that range, satisfactory charge/discharge cycleperformances can be expected. In addition, the area of the interfacebetween the base and a thin active-material film is increased andadhesion to the thin negative-electrode active-material film isimproved. The upper limit of the average surface roughness (Ra) thereofis not particularly limited. However, a current collector base having anaverage surface roughness (Ra) of 1.5 μm or lower is usually employedbecause a foil having a practical thickness for batteries and having anRa exceeding 1.5 μm is generally difficult to procure.

(10-2) Tensile Strength

Tensile strength is a quotient obtained by dividing the maximum tensileforce required before test piece breakage by the sectional area of thetest piece. In invention 1, the tensile strength is determined through ameasurement conducted with the same apparatus and by the same method asthose described in JIS Z 2241 (Method of Metallic-Material TensileTest).

The tensile strength of the current collector base is not particularlylimited. However, it is generally 50 N·mm⁻² or higher, preferably 100N·mm⁻² or higher, more preferably 150 N·mm⁻² or higher. The higher thetensile strength, the more the current collector base is preferred.However, it is desirable that the tensile strength thereof should begenerally 1,000 N·mm⁻² or lower from the standpoint of industrialavailability.

A current collector base having a high tensile strength can be inhibitedfrom cracking with the expansion/contraction of the thin active-materialfilm which occur upon charge/discharge. With this current collectorbase, satisfactory cycle performances can be obtained.

(10-3) 0.2% Proof Stress

The term 0.2% proof stress means the degree of load necessary forimparting a plastic (permanent) deformation of 0.2%. Namely, it meansthat application of that degree of load and subsequent removal thereofresult in a 0.2% deformation. The 0.2% proof stress is determinedthrough a measurement conducted with the same apparatus and by the samemethod as for tensile strength.

The 0.2% proof stress of the current collector base is not particularlylimited. However, the 0.2% proof stress thereof is generally 30 N·mm⁻²or higher, preferably 100 N·mm⁻² or higher, especially preferably 150N/mm² or higher. The higher the 0.2% proof stress, the more the currentcollector base is preferred. However, the 0.2% proof stress thereof isgenerally desirably 900 N·mm⁻² or lower from the standpoint ofindustrial availability.

A current collector base having a high 0.2% proof stress can beinhibited from plastically deforming with the expansion/contraction ofthe thin active-material film which occur upon charge/discharge. Withthis current collector base, satisfactory cycle performances can beobtained.

(10-4) Thickness of Current Collector

The current collector may have any desired thickness. However, thethickness thereof is generally 1 μm or larger, preferably 3 μm orlarger, more preferably 5 μm or larger, and is generally 1 mm orsmaller, preferably 100 μm or smaller, more preferably 50 μm or smaller.

In case where the current collector is thinner than 1 μm, this collectorhas reduced strength and there are hence cases where coating isdifficult. When the current collector is thicker than 100 μm, there arecases where this collector deforms an electrode shape, e.g., a rolledform. The current collector may be in a mesh form.

(11) Thickness Ratio Between Current Collector and Active-Material Layer

The thickness ratio between the current collector and theactive-material layer is not particularly limited. However, the value of“(thickness of the active-material layer on one side just beforeimpregnation with the nonaqueous electrolyte)/(thickness of the currentcollector)” is generally 150 or smaller, preferably 20 or smaller, morepreferably 10 or smaller, and is generally 0.1 or larger, preferably 0.4or larger, more preferably 1 or larger.

When the thickness ratio between the current collector and thenegative-electrode active-material layer exceeds the upper limit of thatrange, there are cases where this current collector heats up due toJoule's heat during high-current-density charge/discharge. When thatratio decreases beyond the lower limit of that range, the proportion byvolume of the current collector to the negative-electrode activematerial increases and this may reduce the capacity of the battery.

(12) Electrode Density

When the negative-electrode active material is used to form anelectrode, the electrode structure is not particularly limited. However,the density of the active material present on the current collector ispreferably 1.0 g·cm⁻³ or higher, more preferably 1.2 g·cm⁻³ or higher,even more preferably 1.3 g·cm⁻³ or higher, especially preferably 1.5g·cm⁻³ or higher, and is preferably 3 g·cm⁻³ or lower, more preferably2.5 g·cm⁻³ or lower, even more preferably 2.2 g·cm⁻³ or lower,especially preferably 2 g·cm⁻³ or lower.

When the density of the active material present on the current collectorexceeds the upper limit of that range, there are cases where bondingbetween the current collector and the negative-electrode active materialis weak and the active material sheds from the electrode. When thedensity thereof is lower than the lower limit of that range, there arecases where electrical conductivity among particles of thenegative-electrode active material decreases and this increases batteryresistance.

(13) Binder

The binder for binding the negative-electrode active material is notparticularly limited so long as it is stable to the nonaqueouselectrolyte and to the solvent to be used for electrode production.

Examples thereof include resinous polymers such as polyethylene,polypropylene, poly(ethylene terephthalate), poly(methyl methacrylate),polyimides, aromatic polyamides, cellulose, and nitrocellulose; rubberypolymers such as SBR (styrene/butadiene rubbers), isoprene rubbers,butadiene rubbers, fluororubbers, NBR (acrylonitrile/butadiene rubbers),and ethylene/propylene rubbers; styrene/butadiene/styrene blockcopolymers or products of hydrogenation thereof; thermoplasticelastomeric polymers such as EPDM (ethylene/propylene/dieneterpolymers), styrene/ethylene/butadiene/styrene copolymers, andstyrene/isoprene/styrene block copolymers and products of hydrogenationthereof; flexible resinous polymers such as syndiotactic1,2-polybutadiene, poly(vinyl acetate), ethylene/vinyl acetatecopolymers, and propylene/a-olefin copolymers; fluorochemical polymerssuch as poly(vinylidene fluoride), polytetrafluoroethylene, fluorinatedpoly(vinylidene fluoride), and polytetrafluoroethylene/ethylenecopolymers; and polymer compositions having the property of conductingalkali metal ions (especially lithium ions). One of these maybe usedalone, or any desired combination of two or more thereof in any desiredproportion may be used.

The kind of the solvent to be used for forming a slurry is notparticularly limited so long as it is a solvent in which thenegative-electrode active material and binder and the thickener andconductive material which are optionally used according to need can bedissolved or dispersed. Either an aqueous solvent or an organic solventmay be used.

Examples of the aqueous solvent include water and alcohols. Examples ofthe organic solvent include N-methylpyrrolidone (NMP),dimethylformamide, dimethylacetamide, methyl ethyl ketone,cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine,N,N-dimethylaminopropylamine, tetrahydrofuran (THF), toluene, acetone,dimethyl ether, hexamethylphosphoramide, dimethyl sulfoxide, benzene,xylene, quinoline, pyridine, methylnaphthalene, and hexane. Especiallywhen an aqueous solvent is used, a dispersant or the like is added incombination with the thickener described above to prepare a slurry usinga latex of, e.g., SBR. One of such ingredients may be used alone, or anydesired combination of two or more thereof in any desired proportion maybe used.

The proportion of the binder to the negative-electrode active materialis generally 0.1% by mass or higher, preferably 0.5% by mass or higher,more preferably 0.6% by mass or higher, and is generally 20% by mass orlower, preferably 15% by mass or lower, more preferably 10% by mass orlower, especially preferably 8% by mass or lower.

In case where the proportion of the binder to the negative-electrodeactive material exceeds the upper limit of that range, the proportion ofthe binder which does not contribute to battery capacity increases andthis may lead to a decrease in battery capacity. When the binderproportion is smaller than the lower limit, there are cases where thenegative electrode has reduced strength and this is undesirable from thestandpoint of battery fabrication step.

Especially when the binder includes a rubbery polymer represented by SBRas the main component, the proportion of this binder to the activematerial is generally 0.1% by mass or higher, preferably 0.5% by mass orhigher, more preferably 0.6% by mass or higher, and is generally 5% bymass or lower, preferably 3% by mass or lower, more preferably 2% bymass or lower.

In the case where the binder includes a fluorochemical polymerrepresented by poly(vinylidene fluoride) as the main component, theproportion of this binder to the active material is 1% by mass orhigher, preferably 2% by mass or higher, more preferably 3% by mass orhigher, and is generally 15% by mass or lower, preferably 10% by mass orlower, more preferably 8% by mass or lower.

A thickener is used generally for the purpose of regulating the slurryviscosity. The thickener is not particularly limited. Examples thereofinclude carboxymethyl cellulose, methyl cellulose, hydroxymethylcellulose, ethyl cellulose, poly(vinyl alcohol), oxidized starch,phosphorylated starch, casein, and salts of these. One of thesethickeners may be used alone, or any desired combination of two or morethereof in any desired proportion may be used.

In the case where such a thickener is further added, the proportion ofthe thickener to the negative-electrode active material may be 0.1% bymass or higher, preferably 0.5% by mass or higher, more preferably 0.6%by mass or higher, and is generally 5% by mass or lower, preferably 3%by mass or lower, more preferably 2% by mass or lower. When theproportion thereof is lower than the lower limit of that range, thereare cases where applicability decreases considerably.

Proportions thereof exceeding the upper limit of that range result in areduced proportion of the active material in the negative-electrodeactive-material layer, and this may pose a problem that battery capacitydecreases and a problem that resistance among the particles of thenegative-electrode active material increases.

<2-4 Positive Electrode>

The positive electrode for use in the nonaqueous-electrolyte secondarybattery of invention 1 is explained below.

<2-4-1 Positive-Electrode Active Material>

Positive-electrode active materials usable in the positive electrode areexplained below.

(1) Composition

The positive-electrode active materials are not particularly limited solong as these are capable of electrochemically occluding/releasinglithium ions. For example, however, a substance containing lithium andat least one transition metal is preferred. Examples thereof includelithium-transition metal composite oxides and lithium-containingtransition metal/phosphoric acid compounds.

The transition metal in the lithium-transition metal composite oxidespreferably is V, Ti, Cr, Mn, Fe, Co, Ni, Cu, or the like. Specificexamples of the composite oxides include lithium-cobalt composite oxidessuch as LiCoO₂, lithium-nickel composite oxides such as LiNiO₂,lithium-manganese composite oxides such as LiMnO₂, LiMn₂O₄, and Li₂MnO₄,and ones formed by partly replacing the transition metal atom(s) as amain component of these lithium-transition metal composite oxides by oneor more other metals, e.g., Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn,Mg, Ga, Zr, Si, etc.

Examples of such compounds formed by replacement includeLiNi_(0.5)Mn_(0.5)O₂, LiNi_(0.85)Co_(0.10)Al_(0.05)O₂,LiNi_(0.33)Co_(0.33)Mn_(0.33)O₂, LiMn_(1.8)Al_(0.2)O₄, andLiMn_(1.5)Ni_(0.5)O₄.

The transition metal in the lithium-containing transitionmetal/phosphoric acid compounds preferably is V, Ti, Cr, Mn, Fe, Co, Ni,Cu, or the like. Specific examples of the compounds include ironphosphate compounds such as LiFePO₄, Li₃Fe₂(PO₄)₃, and LiFeP₂O₇, cobaltphosphate compounds such as LiCoPO₄, and ones formed by partly replacingthe transition metal atom(s) as a main component of theselithium-transition metal/phosphoric acid compounds by one or more othermetals, e.g., Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb,Si, etc.

(2) Surface Coating

Use may be made of a material including any of those positive-electrodeactive materials and, adherent to the surface thereof, a substance(hereinafter abbreviated to “surface-adherent substance”) having acomposition different from that of the substance constituting the corepositive-electrode active material. Examples of the surface-adherentsubstance include oxides such as aluminum oxide, silicon oxide, titaniumoxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide,antimony oxide, and bismuth oxide, sulfates such as lithium sulfate,sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate,and aluminum sulfate, and carbonates such as lithium carbonate, calciumcarbonate, and magnesium carbonate.

Those surface-adherent substances each can be adhered to the surface ofa positive-electrode active material, for example, by: a method in whichthe substance is dissolved or suspended in a solvent and this solutionor suspension is infiltrated into a positive-electrode active materialand then dried; a method in which a precursor for the surface-adherentsubstance is dissolved or suspended in a solvent and this solution orsuspension is infiltrated into a positive-electrode active material andthen heated or otherwise treated to react the precursor; or a method inwhich the substance is added to a precursor for a positive-electrodeactive material and heat-treated together with the precursor.

The mass of the surface-adherent substance adherent to the surface ofthe positive-electrode active material is generally 0.1 ppm or larger,preferably 1 ppm or larger, more preferably 10 ppm or larger, in termsof mass ppm of the positive-electrode active material. The amountthereof is generally 20% or smaller, preferably 10% or smaller, morepreferably 5% or smaller, based on the mass of the positive-electrodeactive material.

The surface-adherent substance serves to inhibit the nonaqueouselectrolyte from undergoing an oxidation reaction on the surface of thepositive-electrode active material, whereby the battery life can beimproved. However, in case where the amount of the substance adhered issmaller than the lower limit of that range, that effect is notsufficiently produced. On the other hand, amounts thereof exceeding theupper limit of that range may result in an increase in resistancebecause the surface-adherent substance inhibits the occlusion/release oflithium ions. Consequently, that range is preferred.

(3) Shape

The shape of the particles of the positive-electrode active material maybe any of massive, polyhedral, spherical, ellipsoidal, platy, acicular,columnar, and other shapes such as those in common use. Preferred ofthese is one in which the primary particles have aggregated to formsecondary particles and these secondary particles have a spherical orellipsoidal shape.

The reasons for that are as follows. In electrochemical elements, theactive material in each electrode usually expands/contracts with thecharge/discharge of the element and, hence, deterioration is apt tooccur, such as active-material breakage and conduction path breakage,due to the stress caused by the expansion/contraction. Consequently, apositive-electrode active material in which the primary particles haveaggregated to form secondary particles is preferable to an activematerial composed of primary particles only since the particles in theformer active material relieve the stress caused byexpansion/contraction to prevent deterioration.

Furthermore, particles of a spherical or ellipsoidal shape arepreferable to particles showing axial orientation, e.g., platy ones,because the former particles are less apt to orient during electrodemolding and hence this electrode is reduced in expansion/contractionduring charge/discharge, and because these particles are apt to beevenly mixed with a conductive material in electrode production.

(4) Tap Density

The tap density of the positive-electrode active material is generally1.3 g·cm⁻³ or higher, preferably 1.5 g·cm⁻³ or higher, more preferably1.6 g·cm⁻³ or higher, especially preferably 1.7 g·cm⁻³ or higher, and isgenerally 2.5 g·cm⁻³ or lower, preferably 2.4 g·cm⁻³ or lower.

By using a metal composite oxide powder having a high tap density, apositive-electrode active-material layer having a high density can beformed. Consequently, when the tap density of the positive-electrodeactive material is lower than the lower limit of that range, not only itis necessary to use a larger amount of a dispersion medium and largeramounts of a conductive material and a binder in forming apositive-electrode active-material layer. There are hence cases wherethe loading of the positive-electrode active material in thepositive-electrode active-material layer is limited, resulting in alimited battery capacity. The higher the tap density, the more thepositive-electrode active material is generally preferred. There is noparticular upper limit on the tap density. However, when the tap densitythereof is lower than that range, there are cases where the diffusion oflithium ions in the positive-electrode active-material layer through thenonaqueous electrolyte as a medium becomes a rate-determining stage andthis is apt to reduce load characteristics.

The tap density of a sample is determined by dropping the sample througha sieve having an opening size of 300 μm into a 20-cm³ tapping cell tofill the capacity of the cell with the sample, subsequently conductingtapping operations 1,000 times over a stroke length of 10 mm using apowder densimeter (e.g., Tap Denser, manufactured by Seishin EnterpriseCo., Ltd.), and determining a density from the resultant volume of thesample and the weight thereof. The tap density determined through thismeasurement is defined as the tap density of the positive-electrodeactive material in invention 1.

(5) Median Diameter d50

The median diameter d50 (secondary-particle diameter in the case wherethe primary particles have aggregated to form secondary particles) ofthe particles of the positive-electrode active material can bedetermined also with a laser diffraction/scattering type particle sizedistribution analyzer.

The median diameter d50 thereof is generally 0.1 μm or larger,preferably 0.5 μm or larger, more preferably 1 μm or larger, especiallypreferably 3 μm or larger, and is generally 20 μm or smaller, preferably18 μm or smaller, more preferably 16 μm or smaller, especiallypreferably 15 μm or smaller. When the median diameter d50 thereof issmaller than the lower limit of that range, there are cases where aproduct having a high bulk density cannot be obtained. When the mediandiameter thereof exceeds the upper limit of that range, lithiumdiffusion in the individual particles requires a longer time and thisresults in a decrease in battery performance. In addition, there arecases where such positive-electrode active-material particles, when usedin producing a positive electrode for batteries, i.e., when the activematerial and other ingredients including a conductive material and abinder are slurried with a solvent and this slurry is applied in athin-film form, pose a problem, for example, that streak lines generate.

It is possible to further improve loading in positive-electrodeproduction by mixing two or more positive-electrode active materialsdiffering in median diameter d50.

In determining median diameter d50, a 0.1% by mass aqueous solution ofsodium hexametaphosphate is used as a dispersion medium. LA-920,manufactured by HORIBA, Ltd., is used as a particle size distributionanalyzer to conduct a five-minute ultrasonic dispersing treatment,before the particles are examined at a measuring refractive index set at1.24.

(6) Average Primary-Particle Diameter

In the case where the primary particles have aggregated to formsecondary particles, the average primary-particle diameter of thispositive-electrode active material is generally 0.01 μm or larger,preferably 0.05 μm or larger, more preferably 0.08 μm or larger,especially preferably 0.1 μm or larger, and is generally 3 μm orsmaller, preferably 2 μm or smaller, more preferably 1 μm or smaller,especially preferably 0.6 μm or smaller. In case where the averageprimary-particle diameter thereof exceeds the upper limit of that range,spherical secondary particles are difficult to form and this adverselyinfluences powder loading or results in a considerably reduced specificsurface area. There may hence be a high possibility that batteryperformances such as output characteristics might decrease. When theaverage primary-particle diameter thereof is smaller than the lowerlimit of that range, crystal growth is usually insufficient and, hence,there are cases where use of this positive-electrode active materialgives a secondary battery having reduced performances, e.g., poorcharge/discharge reversibility.

Average primary-particle diameter is determined through an examinationwith a scanning electron microscope (SEM). Specifically, arbitrarilyselected 50 primary-particle images in a photograph having amagnification of 10,000 diameters each are examined for the length ofthe longest segment of a horizontal line which extends across theprimary-particle image from one side to the other side of the boundary.These measured lengths are averaged, whereby the average value can bedetermined.

(7) BET Specific Surface Area

The BET specific surface area of the positive-electrode active material,in terms of the value of specific surface area as determined by the BETmethod, is generally 0.2 m²·g⁻¹ or larger, preferably 0.3 m²·g⁻¹ orlarger, more preferably 0.4 m²·g⁻¹ or larger, and is generally 4.0m²·g⁻¹ or smaller, preferably 2.5 m²·g⁻¹ or smaller, more preferably 1.5m²·g⁻¹ or smaller. Incase where the BET specific surface area thereof issmaller than the lower limit of that range, battery performances are aptto decrease. In case where the BET specific surface area thereof exceedsthe upper limit of that range, a high tap density is difficult to obtainand there are cases where applicability in forming a positive-electrodeactive-material layer is poor. BET specific surface area is measuredwith a surface area meter (a fully automatic surface area measuringapparatus manufactured by Ohukura Riken Co., Ltd.). The specific surfacearea is determined by preliminarily drying a sample at 150° C. for 30minutes in a nitrogen stream and then measuring the specific surfacearea thereof by the gas-flowing nitrogen adsorption BET one-point methodusing a nitrogen/helium mixture gas precisely regulated so as to have anitrogen pressure of 0.3 relative to atmosphere pressure. The specificsurface area determined through this measurement is defined as the BETspecific surface area of the positive-electrode active material ininvention 1.

(8) Processes for Producing Positive-Electrode Active Material

Processes for producing positive-electrode active materials are notparticularly limited unless the processes depart from the spirit ofinvention 1. Examples thereof include several processes. Techniqueswhich are in general use for producing inorganic compounds may beemployed.

Especially for producing spherical or ellipsoidal active materials,various techniques are usable. Examples thereof include: a method whichcomprises dissolving or pulverizing/dispersing a transition metalsource, e.g., a transition metal nitrate or sulfate, optionally togetherwith a source of other element(s) in a solvent, e.g., water, regulatingthe pH of the solution or dispersion with stirring to produce aspherical precursor, recovering and optionally drying the precursor,subsequently adding thereto a lithium source, e.g., LiOH, Li₂CO₃, orLiNO₃, and burning the mixture at a high temperature to obtain theactive material.

Another example is a method which comprises dissolving orpulverizing/dispersing a transition metal source, e.g., a transitionmetal nitrate, sulfate, hydroxide, or oxide, optionally together with asource of other element(s) in a solvent, e.g., water, drying and formingthe solution or dispersion with a spray dryer or the like to obtain aspherical or ellipsoidal precursor, adding thereto a lithium source,e.g., LiOH, Li₂CO₃, or LiNO₃, and burning the mixture at a hightemperature to obtain the active material.

Still another example is a method which comprises dissolving orpulverizing/dispersing a transition metal source, e.g., a transitionmetal nitrate, sulfate, hydroxide, or oxide, together with a lithiumsource, e.g., LiOH, Li₂CO₃, or LiNO₃, and optionally with a source ofother element(s) in a solvent, e.g., water, drying and forming thesolution or dispersion with a spray dryer or the like to obtain aspherical or ellipsoidal precursor, and burning the precursor at a hightemperature to obtain the active material.

<2-4-2 Electrode Structure and Production Process>

The constitution of the positive electrode to be used in invention 1 anda process for producing the electrode will be described below.

(1) Process for Producing Positive Electrode

The positive electrode is produced by forming a positive-electrodeactive-material layer including particles of a positive-electrode activematerial and a binder on a current collector. The production of thepositive electrode with a positive-electrode active material can beconducted in an ordinary manner. Namely, a positive-electrode activematerial and a binder are mixed together by a dry process optionallytogether with a conductive material, thickener, etc. and this mixture isformed into a sheet and press-bonded to a positive-electrode currentcollector. Alternatively, those materials are dissolved or dispersed ina liquid medium to obtain a slurry and this slurry is applied to apositive-electrode current collector and dried. Thus, apositive-electrode active-material layer is formed on the currentcollector, whereby the positive electrode can be obtained.

The content of the positive-electrode active material in thepositive-electrode active-material layer is generally 10% by mass orhigher, preferably 30% by mass or higher, especially preferably 50% bymass or higher, and is generally 99. 9% by mass or lower, preferably 99%by mass or lower. The reasons for this are as follows. When the contentof the positive-electrode active material in the positive-electrodeactive-material layer is lower than the lower limit of that range, thereare cases where an insufficient electrical capacity results. When thecontent thereof exceeds the upper limit of that range, there are caseswhere the positive electrode has insufficient strength. Onepositive-electrode active-material powder may be used alone in invention1, or any desired combination of two or more positive-electrode activematerials differing in composition or powder properties may be used inany desired proportion.

(2) Conductive Material

As the conductive material, a known conductive material can be used atwill. Examples thereof include metallic materials such as copper andnickel; graphites such as natural graphites and artificial graphites;carbon blacks such as acetylene black; and carbon materials such asamorphous carbon, e.g., needle coke. One of these materials may be usedalone, or any desired combination of two or more thereof in any desiredproportion may be used.

The conductive material may be used so that it is incorporated in thepositive-electrode active-material layer in an amount of generally 0.01%by mass or larger, preferably 0.1% by mass or larger, more preferably 1%by mass or larger, and of generally 50% by mass or lower, preferably 30%by mass or lower, more preferably 15% by mass or lower. When the contentthereof is lower than the lower limit of that range, there are caseswhere electrical conductivity becomes insufficient. Conversely, when thecontent thereof exceeds the upper limit of that range, there are caseswhere battery capacity decreases.

(3) Binder

The binder to be used for producing the positive-electrodeactive-material layer is not particularly limited so long as the binderis stable to the nonaqueous electrolyte and to the solvent to be usedfor electrode production.

In the case where the layer is to be formed through coating fluidapplication, any binder may be used so long as it is a material which issoluble or dispersible in the liquid medium for use in electrodeproduction. Examples thereof include resinous polymers such aspolyethylene, polypropylene, poly(ethylene terephthalate), poly(methylmethacrylate), aromatic polyamides, cellulose, and nitrocellulose;rubbery polymers such as SBR (styrene/butadiene rubbers), NBR(acrylonitrile/butadiene rubbers), fluororubbers, isoprene rubbers,butadiene rubbers, and ethylene/propylene rubbers; thermoplasticelastomeric polymers such as styrene/butadiene/styrene block copolymersor products of hydrogenation thereof, EPDM (ethylene/propylene/dieneterpolymers), styrene/ethylene/butadiene/ethylene copolymers, andstyrene/isoprene/styrene block copolymers or products of hydrogenationthereof; flexible resinous polymers such as syndiotactic1,2-polybutadiene, poly(vinyl acetate), ethylene/vinyl acetatecopolymers, and propylene/a-olefin copolymers; fluorochemical polymerssuch as poly(vinylidene fluoride) (PVdF), polytetrafluoroethylene,fluorinated poly(vinylidene fluoride), andpolytetrafluoroethylene/ethylene copolymers; and polymer compositionshaving the property of conducting alkali metal ions (especially lithiumions). One of these substances may be used alone, or any desiredcombination of two or more thereof in any desired proportion may beused.

The proportion of the binder in the positive-electrode active-materiallayer is generally 0.1% by mass or higher, preferably 1% by mass orhigher, more preferably 3% by mass or higher, and is generally 80% bymass or lower, preferably 60% by mass or lower, more preferably 40% bymass or lower, especially preferably 10% by mass or lower. When theproportion of the binder is lower than the lower limit of that range,there are cases where the positive-electrode active material cannot besufficiently held and the positive electrode has insufficient mechanicalstrength to impair battery performances such as cycle performances. Whenthe proportion thereof is higher than the upper limit of that range,there are cases where such high proportions lead to a decrease inbattery capacity or conductivity.

(4) Liquid Medium

The kind of the liquid medium to be used for forming a slurry is notparticularly limited so long as it is a solvent in which thepositive-electrode active material, conductive material, and binder anda thickener, which is used according to need, can be dissolved ordispersed. Either an aqueous solvent or an organic solvent may be used.

Examples of the aqueous medium include water and mixed solventsincluding an alcohol and water. Examples of the organic medium includealiphatic hydrocarbons such as hexane; aromatic hydrocarbons such asbenzene, toluene, xylene, and methylnaphthalene; heterocyclic compoundssuch as quinoline and pyridine; ketones such as acetone, methyl ethylketone, and cyclohexanone; esters such as methyl acetate and methylacrylate; amines such as diethylenetriamine andN,N-dimethylaminopropylamine; ethers such as diethyl ether andtetrahydrofuran (THF); amides such as N-methylpyrrolidone (NMP),dimethylformamide, and dimethylacetamide; and aprotic polar solventssuch as hexamethylphosphoramide and dimethyl sulfoxide. One of theseliquid media may be used alone, or any desired combination of two ormore thereof in any desired proportion may be used.

(5) Thickener

When an aqueous medium is used as a liquid medium for forming a slurry,it is preferred to use a thickener and a latex of, e.g., astyrene/butadiene rubber (SBR) to prepare a slurry. A thickener is usedgenerally for the purpose of regulating the viscosity of the slurry.

The thickener is not particularly limited unless it considerably lessensthe effects of invention 1. Examples thereof include carboxymethylcellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose,poly(vinyl alcohol), oxidized starch, phosphorylated starch, casein, andsalts of these. One of these thickeners maybe used alone, or any desiredcombination of two or more thereof in any desired proportion may beused.

In the case where such a thickener is further used, the proportion ofthe thickener to the active material desirably is generally 0.1% by massor higher, preferably 0.5% by mass or higher, more preferably 0.6% bymass or higher, and is generally 5% by mass or lower, preferably 3% bymass or lower, more preferably 2% by mass or lower. When the proportionthereof is lower than the lower limit of that range, there are caseswhere applicability decreases considerably. Proportions thereofexceeding the upper limit of that range result in a reduced proportionof the active material in the positive-electrode active-material layer,and this may pose a problem that battery capacity decreases and aproblem that resistance among the particles of the positive-electrodeactive material increases.

(6) Compaction

It is preferred that the positive-electrode active-material layerobtained by coating fluid application and drying should be compactedwith a handpress, roller press, or the like in order to heighten theloading density of the positive-electrode active material. The densityof the positive-electrode active-material layer is preferably 1 g·cm⁻³or higher, more preferably 1.5 g·cm⁻³ or higher, especially preferably 2g·cm⁻³ or higher, and is preferably 4 g·cm⁻³ or lower, more preferably3.5 g·cm⁻³ or lower, especially preferably 3 g·cm⁻³ or lower.

When the density of the positive-electrode active-material layer exceedsthe upper limit of that range, the infiltration of a nonaqueouselectrolyte into around the current collector/active material interfaceis reduced and there are cases where charge/discharge characteristicsespecially at a high current density decrease. When the density thereofis lower than the lower limit of that range, there are cases whereelectrical conductivity among the active-material particles decreases toincrease battery resistance.

(7) Current Collector

The material of the positive-electrode current collector is notparticularly limited, and a known one can be used at will. Examplesthereof include metallic materials such as aluminum, stainless steel,nickel-plated materials, titanium, and tantalum; and carbonaceousmaterials such as carbon cloths and carbon papers. Of these, metallicmaterials are preferred. Especially preferred is aluminum.

In the case of a metallic material, examples of the shape of the currentcollector include metal foils, metal cylinders, metal coils, metalplates, thin metal films, expanded metals, punching metals, and metalfoams. In the case of a carbonaceous material, examples of the collectorshape include carbon plates, thin carbon films, and carbon cylinders. Ofthese, a thin metal film is preferred. The thin film may be in asuitable mesh form.

Although the current collector may have any desired thickness, thethickness thereof is generally 1 μm or larger, preferably 3 μm orlarger, more preferably 5 μm or larger, and is generally 1 mm orsmaller, preferably 100 μm or smaller, more preferably 50 μm or smaller.When the thin film is thinner than the lower limit of that range, thereare cases where this film is deficient in strength required of a currentcollector. When the thin film is thicker than the upper limit of thatrange, there are cases where this film has impaired handleability.

<2-5. Separator>

A separator is generally interposed between the positive electrode andthe negative electrode in order to prevent short-circuiting. In thiscase, the nonaqueous electrolyte of invention 1 is usually infiltratedinto the separator.

The material and shape of the separator are not particularly limited,and known separators can be employed at will unless the effects ofinvention 1 are considerably lessened thereby. In particular, use may bemade of separators constituted of materials stable to the nonaqueouselectrolyte of invention 1, such as resins, glass fibers, and inorganicmaterials. It is preferred to use a separator which is in the form of aporous sheet, nonwoven fabric, or the like and has excellent liquidretentivity.

As the material of the resinous or glass-fiber separators, use can bemade of, for example, polyolefins such as polyethylene andpolypropylene, polytetrafluoroethylene, polyethersulfones, glassfilters, and the like. Preferred of these are glass filters andpolyolefins. More preferred are polyolefins. One of these materials maybe used alone, or any desired combination of two or more thereof in anydesired proportion may be used.

The separator may have any desired thickness. However, the thicknessthereof is generally 1 μm or larger, preferably 5 μm or larger, morepreferably 10 μm or larger, and is generally 50 μm or smaller,preferably 40 μm or smaller, more preferably 30 μm or smaller. When theseparator is thinner than the lower limit of that range, there are caseswhere insulating properties and mechanical strength decrease. When theseparator is thicker than the upper limit of that range, there are caseswhere battery performances including rate characteristics decrease. Inaddition, there also are cases where use of such a separator gives anonaqueous-electrolyte secondary battery which as a whole has a reducedenergy density.

In the case where a porous material such as, e.g., a porous sheet or anonwoven fabric is used as the separator, this separator may have anydesired porosity. However, the porosity thereof is generally 20% orhigher, preferably 35% or higher, more preferably 45% or higher, and isgenerally 90% or lower, preferably 85% or lower, more preferably 75% orlower. In case where the porosity thereof is lower than the lower limitof that range, this separator tends to have increased film resistance,resulting in impaired rate characteristics. In case where the porositythereof is higher than the upper limit of that range, this separatortends to have reduced mechanical strength and reduced insulatingproperties.

The separator may have any desired average pore diameter. However, theaverage pore diameter thereof is generally 0.5 μm or smaller, preferably0.2 μm or smaller, and is generally 0.05 μm or larger. In case where theaverage pore diameter thereof exceeds the upper limit of that range,short-circuiting is apt to occur. When the average pore diameter thereofis smaller than the lower limit of that range, there are cases wherethis separator has increased film resistance, resulting in reduced ratecharacteristics.

On the other hand, examples of the inorganic materials which may be usedinclude oxides such as alumina and silicon dioxide, nitrides such asaluminum nitride and silicon nitride, and sulfates such as bariumsulfate and calcium sulfate. Such materials of a particulate shape orfibrous shape may be used.

With respect to form, a separator of a thin film form may be used, suchas a nonwoven fabric, woven fabric, or microporous film. Suitable onesof a thin film form have a pore diameter of 0.01-1 μm and a thickness of5-50 μm. Besides such a separator in an independent thin film form, usecan be made of a separator obtained by forming a composite porous layercontaining particles of the inorganic material on a surface layer of thepositive electrode and/or negative electrode with a resinous binder.Examples of such separators include a porous layer formed by fixingalumina particles having a 90% particle diameter smaller than 1 μm onboth sides of the positive electrode with a fluororesin as a binder.

<2-6. Battery Design> [Electrode Group]

The electrode group may be either of: one having a multilayer structurein which the positive-electrode plate and negative-electrode platedescribed above have been superposed through the separator describedabove; and one having a wound structure in which the positive-electrodeplate and negative-electrode plate described above have been spirallywound through the separator described above. The proportion of thevolume of the electrode group to the internal volume of the battery(hereinafter referred to as electrode group proportion) is generally 40%or higher, preferably 50% or higher, and is generally 90% or lower,preferably 80% or lower. In case where the electrode group proportion islower than the lower limit of that range, a decrease in battery capacityresults. In case where the electrode group proportion exceeds the upperlimit of that range, this battery has a reduced space volume. There arehence cases where battery heating-up causes members to expand and aliquid component of the electrolyte to have a heightened vapor pressure,resulting in an increased internal pressure. This battery is reduced invarious characteristics including charge/discharge cycling performanceand high-temperature storability, and there are even cases where the gasrelease valve, which releases the gas from the internal pressure, works.

[Current Collector Structure]

The current collector structure is not particularly limited. However,for more effectively realizing the improvement in dischargecharacteristics which is brought about by the nonaqueous electrolyte ofinvention 1, it is preferred to employ a structure reduced in theresistance of wiring parts and joint parts. In the case where internalresistance has been reduced in this manner, use of the nonaqueouselectrolyte of invention 1 produces its effects especiallysatisfactorily.

In the case of electrode groups assembled into the multilayer structuredescribed above, a structure obtained by bundling the metallic coreparts of respective electrode layers and welding the bundled parts to aterminal is suitable. When each electrode has a large area, this resultsin increased internal resistance. In this case, it is preferred todispose two or more terminals in each electrode to reduce theresistance. In the case of an electrode group having the wound structuredescribed above, two or more lead structures may be disposed on each ofthe positive electrode and negative electrode and bundled into aterminal, whereby internal resistance can be reduced.

[Case]

The material of the case is not particularly limited so long as it is asubstance stable to the nonaqueous electrolyte to be used. For example,use may be made of metals such as nickel-plated steel sheets, stainlesssteel, aluminum or aluminum alloys, and magnesium alloys or laminatedfilms constituted of a resin and an aluminum foil. From the standpointof weight reduction, it is preferred to use a metal which is aluminum oran aluminum alloy or a laminated film.

Examples of the case made of such a metal include one of a sealedstructure formed by fusion-bonding metallic members to each other bylaser welding, resistance welding, or ultrasonic welding and one of acaulked structure obtained by caulking members of the metal through aresinous gasket. Examples of the case made of the laminated film includeone of a sealed structure formed by thermally fusion-bonding resinlayers to each other. For the purpose of enhancing sealability, a resindifferent from the resin used in the laminated film may be interposedbetween the resin layers. Especially when resin layers are to bethermally fusion-bonded to each other through a current collectorterminal to produce a sealed structure, metal/resin bonding is necessaryand, hence, a resin having polar groups or a modified resin having polargroups introduced therein is suitable for use as the resin to beinterposed.

[Protective Element]

Examples of the protective element include a PTC (positive temperaturecoefficient), which increases in resistance upon abnormal heating-up orwhen an excessive current flows, a temperature fuse, a thermister, and avalve (current breaker valve) which breaks current flow through thecircuit in abnormal heating-up based on an abrupt increase in theinternal pressure or internal temperature of the battery. It ispreferred to select such a protective element which does not work underordinary high-current use conditions. From the standpoint of highoutput, it is preferred to employ a design which prevents abnormalheating-up and thermal run-away even without a protective element.

[Casing]

The nonaqueous-electrolyte secondary battery of invention 1 is usuallyfabricated by housing the nonaqueous electrolyte, negative electrode,positive electrode, separator, etc. in a casing. This casing is notlimited, and a known one can be employed at will unless thisconsiderably lessens the effects of invention 1.

The casing may be made of any desired material. For example, however,nickel-plated iron, stainless steel, aluminum or an alloy thereof,nickel, titanium, or the like is generally used.

The casing may have any desired shape. For example, the casing may beany of the cylindrical type, prismatic type, laminate type, coin type,large type, and the like.

<Nonaqueous Electrolyte 1-1 and Nonaqueous-Electrolyte Secondary Battery1-1> [1. Nonaqueous Electrolyte 1-1]

The nonaqueous electrolyte of invention 1-1 is a nonaqueous electrolytecomprising a nonaqueous solvent and an electrolyte dissolved therein,and is characterized by containing a monofluorophosphate and/or adifluorophosphate and further containing at least one iron-group elementin an amount of from 0.001 ppm to 1 ppm, excluding 1 ppm, of the wholenonaqueous electrolyte.

<Iron-Group Element>

In the nonaqueous electrolyte of invention 1-1, the coexistence of themonofluorophosphate and/or difluorophosphate with an iron-group elementcontained in a specific concentration produces a synergistic effect,whereby cycle performances especially under the conditions of a highvoltage exceeding 4.2 V, which is the upper-limit use voltage ofordinary nonaqueous-electrolyte secondary batteries, can be greatlyimproved.

Factors in the production of such synergistic effect have not beenelucidated in detail. Although the scope of invention 1-1 is notconstrued as being limited by the factors, it is thought that thefactors are the same as in invention 1.

The content of the iron-group element in invention 1-1 is generally 0.001 ppm or higher, preferably 0. 002 ppm or higher, more preferably0.003 ppm or higher, especially preferably 0.005 ppm or higher, mostpreferably 0.01 ppm or higher, and is generally lower than 1 ppm, basedon the whole nonaqueous electrolyte. When the content thereof is lowerthan the lower limit of that range, there are cases where the effect ofthis invention described above is hardly produced. Incidentally, in thecase where two or more iron-group elements of invention 1-1 are used incombination, these iron-group elements are used so that the totalconcentration thereof is within that range.

In invention 1-1, an iron-group element may be added, during thepreparation of the nonaqueous electrolyte, as, e.g., any of theiron-group element compounds enumerated above. However, an iron-groupelement may be generated in an electrolyte. In the case where aniron-group element has been generated in an electrolyte, the content ofthe iron-group element in the nonaqueous electrolyte can be determinedby the same methods as those described in invention 1. However,especially in microanalysis for determining an iron-group elementconcentration of 1 ppm or lower, “inductively coupled plasma/massspectrometry (ICP-MS)” is effective, which is a combination of ICPemission spectrometry and mass spectrometry.

With respect to the iron-group element, the statements given under<1-4-1. Kind of Iron-group element> in invention 1 apply.

With respect to the compounds for use in the nonaqueous electrolyte ofinvention 1-1, such as the electrolyte, nonaqueous solvent,monofluorophosphate, difluorophosphate, and usable additives, the usableranges, preferred compounds, preferred amounts, production processes,and the like are the same as those described above with regard toinvention 1.

[2. Nonaqueous-Electrolyte Secondary Battery 1-1]

The nonaqueous-electrolyte secondary battery of invention 1-1 includes anegative electrode and a positive electrode which are capable ofoccluding and releasing ions and the nonaqueous electrolyte of invention1-1 described above.

Except for the content of the iron-group element, thenonaqueous-electrolyte secondary battery of invention 1-1 is the same asthe nonaqueous-electrolyte secondary battery of invention 1 describedabove.

<Nonaqueous Electrolyte 2 and Nonaqueous-Electrolyte Secondary Battery2> [1. Nonaqueous Electrolyte for Secondary Battery]

The nonaqueous electrolyte for secondary batteries of invention 2 is anonaqueous electrolyte mainly comprising a nonaqueous solvent and anelectrolyte dissolved therein, and is characterized by containing atleast one compound selected from the group consisting of saturated chainhydrocarbons, saturated cyclic hydrocarbons, aromatic compounds having ahalogen atom, and ethers having a fluorine atom (hereinafter referred toas “compounds of invention 2”), and by further containing amonofluorophosphate and/or a difluorophosphate.

<1-1. Electrolyte>

The electrolyte to be used in the nonaqueous electrolyte of invention 2is not limited, and known ones for use as electrolytes in a targetnonaqueous-electrolyte secondary battery can be employed andincorporated at will. In the case where the nonaqueous electrolyte ofinvention 2 is to be used in nonaqueous-electrolyte secondary batteries,the electrolyte preferably is one or more lithium salts.

Examples of the electrolyte include the same electrolytes as those shownabove with regard to invention 1.

Preferred of these are LiPF₆, LiBF₄, LiCF₃SO₃, LiN(CF₃SO₂)₂,LiN(C₂F₅SO₂)₂, and lithium bis(oxalato)borate. Especially preferred isLiPF₆ or LiBF₄.

In the case of using a combination of electrolytes, the kinds of theelectrolytes and the proportions of the electrolytes are the same asthose described above with regard to invention 1.

Furthermore, the lithium salt concentration, preferred concentration,and the like in the final composition of the nonaqueous electrolyte ofinvention 2 are the same as those described above with regard toinvention 1. The phenomena which occur when the concentration is outsidethe range also are the same as those described above with regard toinvention 1.

Especially in the case where the nonaqueous solvent of the nonaqueouselectrolyte consists mainly of one or more carbonate compounds such asalkylene carbonates or dialkyl carbonates, preferred electrolytes andthe proportion thereof are also the same as those described above withregard to invention 1. The phenomena which occur when the proportion isoutside the range also are the same as those described above with regardto invention 1.

In the case where the nonaqueous solvent of this nonaqueous electrolyteincludes at least 50% by volume cyclic carboxylic acid ester compoundsuch as, e.g., γ-butyrolactone or γ-valerolactone, the kind and contentof the electrolyte may also be the same as those described above withregard to invention 1.

<1-2. Nonaqueous Solvent>

The nonaqueous solvent contained in the nonaqueous electrolyte ofinvention 2 is the same as that described above with regard to thenonaqueous solvent contained in the nonaqueous electrolyte of invention1.

<1-3. Compounds of Invention 2>

The “compounds of invention 2” are at least one compound selected fromthe group consisting of saturated chain hydrocarbons, saturated cyclichydrocarbons, aromatic compounds having a halogen atom, and ethershaving a fluorine atom. Of these, saturated cyclic hydrocarbons orethers having a fluorine atom are prepared because these compounds bringabout a large increase in output characteristics. One compound selectedfrom the compounds of invention 2 may be used alone, or any desiredcombination of two or more compounds selected therefrom may be used.Each of the compounds constituting the “compounds of invention 2” ininvention 2 are explained below in more detail.

<1-3-1. Saturated Chain Hydrocarbons>

The saturated chain hydrocarbons are not particularly limited. From thestandpoint of handleability, however, ones which are liquid at ordinarytemperature and ones which have low toxicity are preferred. From thestandpoint of battery characteristics, ones having a relatively lowmolecular weight are preferred. More specifically, ones having 5-20carbon atoms are preferred, and ones having 7-16 carbon atoms areespecially preferred.

For example, pentane, hexane, heptane, octane, nonane, decane, undecane,dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane,octadecene, nonadecane, or eicosane is preferred. Especially preferredis heptane, octane, nonane, decane, undecane, dodecane, tridecane,tetradecane, pentadecane, or hexadecane. These saturated chainhydrocarbons may be linear ones or branched ones. These saturated chainhydrocarbons may be used alone or in any desired combination of two ormore thereof.

<1-3-2. Saturated Cyclic Hydrocarbons>

The saturated cyclic hydrocarbons are not particularly limited. However,ones having 3-20 carbon atoms are preferred, and ones having 5-16 carbonatoms are especially preferred.

For example, cyclopropane, cyclobutane, cyclopentane, cyclohexane,cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane,cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane,cyclohexadecane, cycloheptadecane, cyclooctadecane, cyclononadecane, orcycloeicosane is preferred. Especially preferred is cyclopentane,cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane,cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane,cyclopentadecane, or cyclohexadecane.

These saturated cyclic hydrocarbons may have one or more linear alkylgroups in the molecule. Although such linear alkyl groups are notlimited, alkyl groups having 1-8 carbon atoms are preferred. Examplesthereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, oroctyl. A most preferred example of the saturated cyclic hydrocarbons iscyclohexane. Those saturated cyclic hydrocarbons may be used alone or inany desired combination of two or more thereof.

<1-3-3. Aromatic Compounds Having Halogen Atom(s)>

The aromatic compounds having a halogen atom are not particularlylimited. However, the halogen atoms preferably are fluorine or chlorineatoms, and especially preferably are fluorine atoms. The halogen atomsmay have been directly bonded to the aromatic ring, or may be containedin a substituent.

Examples of the aromatic compounds having a halogen atom includefluorobenzene, chlorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene,1,4-difluorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene,1,4-dichlorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene,1,2,4,6-tetrafluorobenzene, hexafluorobenzene, 2-fluorotoluene,3-fluorotoluene, 4-fluorotoluene, fluoromethylbenzene,difluoromethylbenzene, trifluoromethylbenzene,2-fluoro-1-trifluoromethylbenzene, 4-fluoro-1-trifluoromethylbenzene,2-fluorobiphenyl, o-cyclohexylfluorobenzene, andp-cyclohexylfluorobenzene. Preferred is fluorobenzene, 2-fluorotoluene,4-fluorotoluene, or trifluoromethylbenzene. These “aromatic compoundshaving a halogen atom” may be used alone or in any desired combinationof two or more thereof.

<1-3-4. Ethers Having Fluorine Atom(s)>

The ethers having a fluorine atom are not particularly limited. Whenethers are expressed by the general formula “R⁵—O—R⁶”, then the “ethershaving a fluorine atom” are compounds in which at least either of thegroups R⁵ and R⁶ contain one or more fluorine atoms. On the assumptionthat R⁵ is the group containing one or more fluorine atoms, it ispreferred that the R⁵ should be an alkyl group having 1-20 carbon atomsand substituted with 1-30 fluorine atoms.

Preferred examples of such ethers include fluoromethyl, difluoromethyl,trifluoromethyl; 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl,1,2-difluoroethyl, 2,2-difluoroethyl, 1,1,2-trifluoroethyl,1,2,2-trifluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl,1,2,2,2-tetrafluoroethyl, pentafluoroethyl; 3-fluoropropyl,3,3-difluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl,heptafluoropropyl; 4-fluorobutyl, 4,4-difluorobutyl,4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl,2,2,3,3,4,4,4-heptafluorobutyl, nonafluorobutyl; 5-fluoropentyl,5,5-difluoropentyl, 5,5,5-trifluoropentyl, 4,4,5,5,5-pentafluoropentyl,3,3,4,4,5,5,5-heptafluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl,undecafluoropentyl; 6-fluorohexyl, 6,6-difluorohexyl,6,6,6-trifluorohexyl, and tridecafluorohexyl.

It is preferred that R⁶ should be an alkyl group which has 1-20 carbonatoms and may have been substituted with substituents, e.g., halogens.Besides the fluorine-containing alkyl groups enumerated above withregard to R⁵, examples of R⁶ include ordinary chain alkyl groups (whichmaybe linear or branched), such as methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, alkyl groupscontaining a halogen other than fluorine, and cycloalkyl groups such ascyclohexyl.

Specific examples of the fluorine-containing ethers include2-fluoroethyl ethyl ether, bis(2-fluoroethyl) ether,2,2,2-trifluoroethyl ethyl ether, bis(2,2,2-trifluoroethyl) ether,bis(pentafluoroethyl) ether, 3-fluoropropyl methyl ether, 3-fluoropropylfluoromethyl ether, 3-fluoropropyl trifluoromethyl ether, 3-fluoropropylethyl ether, 3-fluoropropyl-2-fluoroethyl ether, 3,3,3-trifluoropropylmethyl ether, 3,3,3-trifluoropropyl ethyl ether,3,3,3-trifluoropropyl-2-fluoroethyl ether,3,3,3-trifluoropropyl-2,2,2-trifluoroethyl ether, heptafluoropropylmethyl ether, heptafluoropropyl ethyl ether,heptafluoropropyl-2,2,2-trifluoroethyl ether, heptafluoropropylpentafluoroethyl ether, 4-fluorobutyl methyl ether, 4-fluorobutyl ethylether, 4-fluorobutyl-2-fluoroethyl ether, 4,4,4-trifluorobutyl ethylether, 4,4,4-trifluorobutyl-2-fluoroethyl ether,4,4,4-trifluorobutyl-2,2,2-trifluoroethyl ether, 4,4,4-trifluorobutylpentafluoroethyl ether, nonafluorobutyl methyl ether, nonafluorobutylethyl ether, nonafluorobutyl-2-fluoroethyl ether,nonafluorobutyl-2,2,2-trifluoroethyl ether, and nonafluorobutylpentafluoroethyl ether.

Preferred of these is 2-fluoroethyl ethyl ether,bis(2-fluoroethyl)ether, 2,2,2-trifluoroethyl ethyl ether,bis(2,2,2-trifluoroethyl)ether, heptafluoropropyl ethyl ether, ornonafluorobutyl ethyl ether. These fluorine-containing ethers may beused alone or in any desired combination of two or more thereof.

<1-3-5. Content>

The content of the “compounds of invention 2” based on the wholenonaqueous electrolyte is not particularly limited. From the standpointof battery characteristics, however, the content thereof is preferably0.01% by mass or higher, more preferably 0.1% by mass or higher,especially preferably 0.3% by mass or higher. On the other hand, theupper limit thereof is preferably 15% by mass or lower, more preferably12% by mass or lower, especially preferably 10% by mass or lower. Whenthe content thereof is too low, there are cases where the excellenteffect of improving “output” and “output after cycling” possessed by the“monofluorophosphate and/or difluorophosphate” which will be describedbelow cannot be enhanced.

<1-4. Monofluorophosphate and Difluorophosphate>

The “monofluorophosphate and/or difluorophosphate” to be used ininvention 2 is the same as in invention 1. Preferred ranges also are thesame as in invention 1.

<1-4-1. Monofluorophosphoric Acid Metal Salt and Difluorophosphoric AcidMetal Salt>

First, in the case where the monofluorophosphate and difluorophosphatein invention 2 are a salt of one or more monofluorophosphate ions or oneor more difluorophosphate ions with one or more specific metal ions,examples of this salt include the same salts as those enumerated abovewith regard to invention 1.

<1-4-2. Monofluorophosphoric Acid Quaternary Onium Salt andDifluorophosphoric Acid Quaternary Onium Salt>

Next, in the case where the monofluorophosphate and difluorophosphate ininvention 2 are a salt of a monofluorophosphate ion or difluorophosphateion with a quaternary onium, examples of this salt include the samesalts as those enumerated above with regard to invention 1.

<1-4-3. Content, Detection (Derivation of Containment), Technical Range,Etc.>

In the nonaqueous electrolyte of invention 2, one monofluorophosphate ordifluorophosphate only may be used or any desired combination of two ormore monofluorophosphates and/or difluorophosphates maybe used in anydesired proportion. However, from the standpoint of efficientlyoperating the nonaqueous-electrolyte secondary battery, it is preferredto use one monofluorophosphate or difluorophosphate.

The molecular weight of the monofluorophosphate or difluorophosphate,processes for producing the salt, proportion of the salt in thenonaqueous electrolyte, etc. are the same as those described above withregard to invention 1.

Furthermore, the time at which a monofluorophosphate ordifluorophosphate is detected (the time at which the salt is contained),the place into which the salt is incorporated first (derivation ofcontainment), means of incorporating the salt, detection places based onwhich the salt is considered to be contained (or have been contained) inthe nonaqueous electrolyte, etc. are also the same as those describedabove with regard to invention 1.

<1-5. Additives>

The nonaqueous electrolyte of invention 2 may contain various additivesso long as these additives do not considerably lessen the effects ofinvention 2. In the case where additives are additionally incorporatedto prepare the nonaqueous electrolyte, conventionally known additivescan be used at will. One additive may be used alone, or any desiredcombination of two or more additives in any desired proportion may beused.

Examples of the additives include overcharge inhibitors and aids forimproving capacity retention after high-temperature storage and cycleperformances. It is preferred to add a carbonate having at least one ofan unsaturated bond and a halogen atom (hereinafter sometimes referredto as “specific carbonate”) as an aid for improving capacity retentionafter high-temperature storage and cycle performances, among thoseadditives.

<1-5-1. Specific Carbonate>

Examples of the specific carbonate include the same carbonates as thoseenumerated above with regard to invention 1.

<1-5-2. Other Additives>

Additives other than the specific carbonate are explained below.Examples of the additives other than the specific carbonate includeovercharge inhibitors and aids for improving capacity retention afterhigh-temperature storage and cycle performances.

<1-5-2-1. Overcharge Inhibitors>

Examples of the overcharge inhibitors include aromatic compoundsincluding: toluene and derivatives thereof, such as toluene and xylene;

-   unsubstituted biphenyl or alkyl-substituted biphenyl derivatives,    such as biphenyl, 2-methylbiphenyl, 3-methylbiphenyl, and    4-methylbiphenyl;-   unsubstituted terphenyls or alkyl-substituted terphenyl derivatives,    such as o-terphenyl, m-terphenyl, and p-terphenyl;-   partly hydrogenated unsubstituted terphenyls or partly hydrogenated    alkyl-substituted terphenyl derivatives;-   cycloalkylbenzenes and derivatives thereof, such as    cyclopentylbenzene and cyclohexylbenzene;-   alkylbenzene derivatives having one or more tertiary carbon atoms    directly bonded to the benzene ring, such as cumene,    1,3-diisopropylbenzene, and 1,4-diisopropylbenzene;-   alkylbenzene derivatives having a quaternary carbon atom directly    bonded to the benzene ring, such as t-butylbenzene, t-amylbenzene,    and t-hexylbenzene; and-   aromatic compounds having an oxygen atom, such as diphenyl ether and    dibenzofuran.

One of those overcharge inhibitors may be used alone, or any desiredcombination of two or more thereof may be used in any desiredproportion. In the case of employing any desired combination, compoundsin the same class among those enumerated above may be used incombination or compounds in different classes may be used incombination.

Examples of the case where compounds in different classes are used incombination are the same as in invention 1.

In the case where the nonaqueous electrolyte of invention 2 contains anovercharge inhibitor, the concentration and effect thereof are the sameas in invention 1.

<1-5-2-2. Aids>

Examples of the aids for improving capacity retention afterhigh-temperature storage and cycle performances include: the anhydridesof dicarboxylic acids such as succinic acid, maleic acid, and phthalicacid; carbonate compounds other than the specific carbonates, such aserythritan carbonate and spiro-bis-dimethylene carbonate;sulfur-containing compounds such as ethylene sulfite,1,3-propanesultone, 1,4-butanesultone, methyl methanesulfonate,busulfan, sulfolane, sulfolene, dimethyl sulfone, diphenyl sulfone,methyl phenyl sulfone, dibutyl disulfide, dicyclohexyl disulfide,tetramethylthiuram monosulfide, N,N-dimethylmethanesulfonamide, andN,N-diethylmethanesulfonamide; nitrogen-containing compounds such as1-methyl-2-pyrrolidinone, 1-methyl-2-piperidone,3-methyl-2-oxazolidinone, and 1,3-dimethyl-2-imidazolidinone, andN-methylsuccinimide.

<1-6. Process for Producing Nonaqueous Electrolyte>

For producing nonaqueous electrolyte 2, the same process as in invention1 can be used.

[2. Nonaqueous-Electrolyte Secondary Battery]

The nonaqueous-electrolyte secondary battery of invention 2 includes: anegative electrode and a positive electrode which are capable ofoccluding and releasing ions; and the nonaqueous electrolyte ofinvention 2 described above.

The following are the same as those described above with regard toinvention 1: battery constitution; negative electrode; carbonaceousmaterial; constitution and properties of carbonaceous negative electrodeand method of preparation thereof; metal compound material, constitutionand properties of negative electrode employing metal compound material,and method of preparation thereof; positive electrode; separator;battery design; and the like.

<Function>

Use of the nonaqueous electrolyte according to invention 2, whichcontains both of a compound selected from the “compounds of invention 2”and a monofluorophosphate and/or difluorophosphate, enables thenonaqueous-electrolyte secondary battery to show high outputcharacteristics. Although the mechanism by which such effect is broughtabout is not clear, the following is thought. However, invention 2should not be construed as being limited by the following mechanism. Aswill be demonstrated by “Comparative Example 6 for Invention 2” givenlater, a certain degree of high output is obtained even when adifluorophosphate only is contained. On the other hand, when a compoundselected from the “compounds of invention 2” is incorporated alone, noclear effect is observed, as will be demonstrated by “ComparativeExamples 2 to 5 for Invention 2”. Consequently, it is thought that thecompound selected from the “compounds of invention 2” in invention 2helps the effect of the monofluorophosphate and difluorophosphate.Specifically, it is thought that the compound leads themonofluorophosphate and/or difluorophosphate, which improves outputbased on interaction with each electrode, to inner parts of theelectrode active-material layer to enhance the interaction with theelectrode.

<Nonaqueous Electrolyte 3 and Nonaqueous-Electrolyte Secondary Battery3> [1. Nonaqueous Electrolyte]

Like ordinary nonaqueous electrolytes, the nonaqueous electrolyte ofinvention 3 includes an electrolyte and a nonaqueous solvent containingthe electrolyte dissolved therein.

<1-1. Electrolyte>

The electrolyte to be contained in the nonaqueous electrolyte ofinvention 3 is not limited, and known ones for use as electrolytes in atarget nonaqueous-electrolyte secondary battery can be employed andmixed at will. In the case where the nonaqueous electrolyte of invention3 is to be used in lithium ion secondary batteries, it is preferred touse one or more lithium salts.

Examples of the electrolyte include the same electrolytes as those shownabove with regard to invention 1.

Preferred of these are LiPF₆, LiBF₄, LiCF₃SO₃, LiN(CF₃SO₂)₂,LiN(C₂F₅SO₂)₂, and lithium bis(oxalato)borate. Especially preferred isLiPF₆ or LiBF₄.

In the case of using a combination of electrolytes, the kinds of theelectrolytes and the proportions of the electrolytes are the same asthose described above with regard to the nonaqueous electrolyte ofinvention 1.

Furthermore, the lithium salt concentration, preferred concentration,and the like in the final composition of the nonaqueous electrolyte ofinvention 3 are the same as those described above with regard tononaqueous electrolyte 1. The phenomena which occur when theconcentration is outside the range also are the same as those describedabove with regard to nonaqueous electrolyte 1.

Especially in the case where the nonaqueous solvent of the nonaqueouselectrolyte consists mainly of one or more carbonate compounds such asalkylene carbonates or dialkyl carbonates, preferred electrolytes andthe proportion thereof are also the same as those described above withregard to the nonaqueous electrolyte of invention 1. The phenomena whichoccur when the proportion is outside the range also are the same asthose described above with regard to the nonaqueous electrolyte ofinvention 1.

In the case where the nonaqueous solvent of this nonaqueous electrolyteincludes at least 50% by volume cyclic carboxylic acid ester compoundsuch as, e.g., γ-butyrolactone or γ-valerolactone, the kind and contentof the electrolyte may also be the same as those described above withregard to invention 1.

<1-2. Compound Represented by General Formula (1)>

In invention 3, the compound represented by general formula (1) is thefollowing compound.

[R¹, R², R³, and R⁴ each independently are an organic group or a halogenatom, provided that at least one of the R¹, R², R³, and R⁴ is a group inwhich the atom directly bonded to the X is a heteroatom and that two ormore of the R¹, R², R³, and R⁴ may be the same. X is an atom other thana carbon atom.]

In general formula (1) in invention 3, X is not particularly limited solong as it is an atom other than a carbon atom. However, in view ofstability in the nonaqueous electrolyte, etc., a silicon atom or atitanium atom is preferred.

R¹, R², R³, and R⁴ each independently represent an organic group or ahalogen atom. The organic group is not particularly limited. Examples ofthe “organic group” in which the atom directly bonded to the X is acarbon atom include alkyl, alkenyl, and alkynyl groups which may haveone or more substituents. The number of carbon atoms of each of theseorganic groups is more preferably 1-10.

Specifically, examples of the alkyl groups include methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl,2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,1,2-dimethylpropyl, and neopentyl. Examples of the alkenyl groupsinclude vinyl, allyl, isopropenyl, 1-propenyl, butenyl, butadienyl, andpentenyl. Examples of the alkynyl groups include ethynyl, 1-propionyl,1-butynyl, 1-pentynyl, 2-propionyl, 2-butynyl, and 3-butynyl.

The substituents of these groups are not particularly limited. Examplesthereof include a fluorine atom, chlorine atom, methacryloxy, mercapto,alkylamino groups, arylamino groups, glycidoxy, benzoyloxy, andacetyloxy.

Examples of the halogen atom include fluorine, chlorine, bromine, andiodine atoms. Especially preferred is a chlorine atom or a fluorineatom.

At least one of the R¹, R², R³, and R⁴ is a group in which the atomdirectly bonded to the X is a heteroatom. The heteroatom is notparticularly limited so long as it is an atom other than a carbon atom.However, B, N, O, P, S, or halogen atoms are preferred because theseatoms bring about high reactivity and, as a result, can impart excellentcycle performances. Especially preferred of these is a halogen atom,oxygen atom, or nitrogen atom.

In the case where the “group in which the atom directly bonded to the Xis a heteroatom” is a group in which the heteroatom is an oxygen atom,examples of this group include alkoxy groups such as methoxy, ethoxy,propoxy, butoxy, pentoxy, isopropoxy, 1-methylpropoxy, 2-methylpropoxy,and tert-butoxy; and benzoyloxy and acetyloxy. In the case where theheteroatom is a nitrogen atom, examples of the group includedimethylamino, diethylamino, and ethylmethylamino. Of these, alkoxygroups such as methoxy, ethoxy, propoxy, and butoxy are more preferredfor the same reason as shown above.

The “group in which the atom directly bonded to the X is a heteroatom”maybe a halogen atom. In this case, the halogen atom preferably is afluorine atom, chlorine atom, bromine atom, or iodine atom. A chlorineatom is more preferred for the same reason as shown above.

The “group in which the atom directly bonded to the X is a heteroatom”may have one or more substituents. However, an alkoxy group having nosubstituents or a chlorine atom is especially preferred for the samereason as shown above.

In the compound represented by general formula (1) in invention 3, atleast one of the R¹, R², R³, and R⁴ is a group in which the atomdirectly bonded to the X is a heteroatom. It is, however, preferred thatat least two of the R¹, R², R³, and R⁴ each should be a group in whichthe atom directly bonded to the X is a heteroatom. It is especiallypreferred that two or three of the R¹, R², R³, and R⁴ each should be a“group in which the atom directly bonded to the X is a heteroatom”. Inthis case, a nonaqueous electrolyte for secondary batteries which hasexcellent cycle performances can be obtained.

The reasons for this are as follows. When an electrode interacts withthe “groups in which the atom directly bonded to the X is a heteroatom”,there are cases where the interaction therebetween is weak when thenumber of the “groups in which the atom directly bonded to the X is aheteroatom” is too small. On the other hand, especially when all of thefour groups R¹, R², R³, and R⁴ are “groups in which the atom directlybonded to the X is a heteroatom”, there are cases where sufficientelectrode stabilization cannot be attained because there is no groupwhich interacts with the nonaqueous electrolyte.

In general formula (1), two or more of the R¹, R², R³, and R⁴ may be thesame.

Examples of the compound represented by general formula (1) in invention3 include vinyltrichlorosilane, vinyltrimethoxysilane,vinyltriethoxysilane, vinyltris(β-methoxy-ethoxy)silane,3-methacryloxypropyltriethoxysilane,3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropylmethyldiethoxysilane,3-methacryloxypropyltrimethoxysilane,2-methacryloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane,3-mercaptopropyltrimethoxysilane, N-(2-aminoethyl)-γaminopropyltrimethoxysilane, N-(2-aminoethyl)-γaminopropyltriethoxysilane, N-(2-aminoethyl)-γaminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane,3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,(2-n-butoxycarbonylbenzoyloxy)tributoxytitanium, diisopropoxytitaniumdiisostearate, and titanium stearate. One of these compounds maybe usedalone, or two or more thereof may be used in combination.

In the case where X is titanium, organotitanium chelate compounds andthe like are also preferred in which a chelating compound such as, e.g.,acetylacetone or an alkyl acetoacetate has coordinated to the titanium.One of these compounds may be used alone, or two or more thereof maybeused in combination.

<1-3. Compound Represented by General Formula (2)>

In invention 3, the compound represented by general formula (2) is thefollowing compound.

[R⁵, R⁶, and R⁷ each independently are an organic group or a halogenatom, provided that at least one of R⁵, R⁶, and R⁷ is a group in whichthe atom directly bonded to the Y is a heteroatom (including a halogenatom) and that two or more of the R⁵, R⁶, and R⁷ may be the same. Y isan atom other than a carbon atom.]

R⁵, R⁶, and R⁷ in general formula (2) in invention 3 each independentlyare an organic group or a halogen atom. With respect to this organicgroup or halogen atom, the same statements given above with regard togeneral formula (1) hold. Furthermore, at least one of the R⁵, R⁶, andR⁷ is a group in which the atom directly bonded to the Y is aheteroatom. With respect to the “heteroatom” and the “group in which theatom directly bonded to the Y is a heteroatom” also, the same statementsgiven above with regard to general formula (1) hold.

Y in general formula (2) in invention 3 preferably is an aluminum atomin view of stability in the electrolyte, etc.

Although at least one of the R⁵, R⁶, and R⁷ is a “group in which theatom directly bonded to the Y is a heteroatom”, it is preferred thatjust two of these should be ones in which the atom directly bonded tothe Y is a heteroatom. In this case, a nonaqueous electrolyte forsecondary batteries which has excellent cycle performances can beobtained.

The reasons for this are as follows. When an electrode interacts withthe “groups in which the atom directly bonded to the Y is a heteroatom”,there are cases where the interaction therebetween is too weak when theproportion of the “group in which the atom directly bonded to the Y is aheteroatom” in the R⁵, R⁶, and R⁷ is too small. On the other hand, whenall of the three groups R¹, R², and R³ are “groups in which the atomdirectly bonded to the Y is a heteroatom”, there are cases wheresufficient electrode stabilization cannot be attained because there isno group which interacts with the nonaqueous electrolyte.

In general formula (2), two or more of the R⁵, R⁶, and R⁷ may be thesame.

Examples of the compound represented by general formula (2) in invention3 include acetylacetonatodiisopropylaluminum. One of such compounds maybe used alone, or two or more thereof may be used in combination.

Examples thereof further include organoaluminum chelate compounds inwhich a chelating compound other than acetylacetone as in the exampleshown above, such as, e.g., an alkyl acetoacetate, has coordinated tothe aluminum. One of these compounds may be used alone, or two or morethereof may be used in combination.

<1-4. Content of Compound Represented by General Formula (1) andCompound Represented by General Formula (2)>

It is preferred that the compound represented by general formula (1) ininvention 3 and the compound represented by general formula (2) ininvention 3 should be contained in a total proportion of from 0.001% bymass to 10% by mass based on the whole nonaqueous electrolyte. The totalproportion of these compounds is especially preferably from 0.01% bymass to 5% by mass. In case where the proportion of these compounds tothe whole nonaqueous electrolyte is too low, the effect of the additionthereof cannot be sufficiently produced. There are hence cases where anonaqueous electrolyte for secondary batteries which has excellent cycleperformances cannot be obtained. On the other hand, when the proportionthereof is too high, there are cases where battery capacity is impairedby the reaction of the compounds themselves.

It is preferred that in preparing the nonaqueous electrolyte, thecompounds represented by general formula (1) or general formula (2)should be incorporated in mass amounts corresponding to from 0.001% bymass to 10% by mass in terms of the total amount thereof based on thewhole nonaqueous electrolyte. Especially preferably, the compounds areincorporated in mass amounts corresponding to form 0.01% by mass to 5%by mass to prepare the nonaqueous electrolyte.

<1-5. Nonaqueous Solvent>

The nonaqueous solvent contained in the nonaqueous electrolyte ofinvention 3 is the same as the nonaqueous solvent contained in thenonaqueous electrolyte of invention 1.

<1-6. Monofluorophosphate and Difluorophosphate>

The nonaqueous electrolyte of invention 3 contains a monofluorophosphateand/or difluorophosphate as an essential component. The“monofluorophosphate and/or difluorophosphate” to be used in invention 3is the same as the “monofluorophosphate and/or difluorophosphate” usedin invention 1.

<1-6-1. Monofluorophosphoric Acid Metal Salt and Difluorophosphoric AcidMetal Salt>

Also in the case where the monofluorophosphate and difluorophosphate ininvention 3 are a salt of one or more monofluorophosphate ions or one ormore difluorophosphate ions with one or more specific metal ions(respectively referred to as “monofluorophosphoric acid metal salt” and“di fluorophosphoric acid metal salt”), these salts are the same as ininvention 1.

<1-6-2. Monofluorophosphoric Acid Quaternary Onium Salt andDifluorophosphoric Acid Quaternary Onium Salt>

Also in the case where the monofluorophosphate and difluorophosphate ininvention 3 are a salt of a monofluorophosphate ion or difluorophosphateion with a quaternary onium (respectively referred to as“monofluorophosphoric acid quaternary onium salt” and“difluorophosphoric acid quaternary onium salt”), these salts are thesame as in invention 1.

<1-6-3. Content, Detection (Derivation of Containment), Technical Range,Etc.>

In the nonaqueous electrolyte of invention 3, one monofluorophosphate ordifluorophosphate only may be used or any desired combination of two ormore monofluorophosphates and/or difluorophosphates may be used in anydesired proportion. However, from the standpoint of efficientlyoperating the nonaqueous-electrolyte secondary battery, it is preferredto use one monofluorophosphate or difluorophosphate.

The molecular weight of the monofluorophosphate or difluorophosphate,processes for producing the salt, proportion of the salt in thenonaqueous electrolyte, etc. are the same as those described above withregard to invention 1.

Furthermore, the time at which a monofluorophosphate ordifluorophosphate is detected (the time at which the salt is contained),the place into which the salt is incorporated first (derivation ofcontainment), means of incorporating the salt, detection places based onwhich the salt is considered to be contained (or have been contained) inthe nonaqueous electrolyte, etc. are also the same as those describedabove with regard to invention 1.

<1-7. Additives>

The nonaqueous electrolyte of invention 3 may contain various additivesso long as these additives do not considerably lessen the effects ofinvention 3. In the case where additives are additionally incorporatedto prepare the nonaqueous electrolyte, conventionally known additivescan be used at will. One additive may be used alone, or any desiredcombination of two or more additives in any desired proportion may beused.

Examples of the additives include overcharge inhibitors and aids forimproving capacity retention after high-temperature storage and cycleperformances. It is preferred to add a carbonate having at least one ofan unsaturated bond and a halogen atom (hereinafter sometimes referredto as “specific carbonate”) as an aid for improving capacity retentionafter high-temperature storage and cycle performances, among thoseadditives.

<1-7-1. Specific Carbonate>

Examples of the specific carbonate are the same as in invention 1.

<1-7-2. Other Additives>

Examples of additives other than the specific carbonate includeovercharge inhibitors and aids for improving capacity retention afterhigh-temperature storage and cycle performances. Examples of theovercharge inhibitors, the concentration and effect thereof, andexamples of the aids are the same as those described above with regardto invention 1.

<1-6. Process for Producing Nonaqueous Electrolyte>

For producing nonaqueous electrolyte 3, the same process as in invention1 can be used.

[2. Nonaqueous-Electrolyte Secondary Battery]

The nonaqueous-electrolyte secondary battery of invention 3 isconstituted of the nonaqueous electrolyte of invention 3 described aboveand a positive electrode and a negative electrode which are capable ofoccluding and releasing ions. The nonaqueous-electrolyte secondarybattery of invention 3 may have other constitutions.

The following are the same as those described above with regard toinvention 1: battery constitution; negative electrode; carbonaceousmaterial; constitution and properties of carbonaceous negative electrodeand method of preparation thereof; metal compound material, constitutionand properties of negative electrode employing metal compound material,and method of preparation thereof; positive electrode; separator;battery design; and the like. The negative-electrode active material isnot particularly limited so long as the active material is capable ofelectrochemically occluding/releasing lithium ions. Examples thereofinclude a carbonaceous material, an alloy material, and alithium-containing metal composite oxide material. Examples of thecarbonaceous material, alloy material, metal compound material, andlithium-containing metal composite oxide material, the constitution andproperties of negative electrodes respectively employing thesematerials, and the method of preparation thereof are the same as thosedescribed above with regard to invention 1.

<Treatment of Electrode>

It is preferred that the nonaqueous electrolyte of invention 3 should beused in a nonaqueous-electrolyte secondary battery including a positiveelectrode or negative electrode which has been treated with one or morecompounds represented by general formula (1) and/or general formula (2)in invention 3, from the standpoints, for example, that the batteryprovided can have excellent cycle performances and that reactionsoccurring on the electrode surface can be inhibited.

Methods for treating a positive electrode or negative electrode with atleast one member selected from the group consisting of compoundsrepresented by general formula (1) and compounds represented by generalformula (2) in invention 3 are not particularly limited. However, it ispreferred to use a method in which a compound represented by generalformula (1) and/or a compound represented by general formula (2) ininvention 3 is evenly distributed on the electrode surface.Specifically, a method in which the electrode is immersed in or coatedwith a liquid obtained by dissolving or dispersing a compoundrepresented by general formula (1) and/or a compound represented bygeneral formula (2) according to invention 3 in a solvent or dispersionmedium is especially preferred.

To treat a positive-electrode active material or a negative-electrodeactive material is also possible. This case also is included in theconception “treatment of a positive electrode or a negative electrode”in invention 3. In this case, the treatment can be accomplished bymixing a positive-electrode active material or negative-electrode activematerial with a liquid obtained by dissolving or dispersing a compoundrepresented by general formula (1) and/or a compound represented bygeneral formula (2) according to invention 3 in a solvent or dispersionmedium. The active material which has been thus treated may be used toproduce a positive electrode or negative electrode. It is preferred thatthe electrode which has been treated should be subjected to a heattreatment in order to enhance interaction between the compoundrepresented by general formula (1) and/or compound represented bygeneral formula (2) in invention 3 and the electrode or electrode activematerial. The heat treatment is conducted preferably at 45° C.-300° C.,more preferably at 60° C.-200° C.

<Nonaqueous Electrolyte 4 and Nonaqueous-Electrolyte Secondary Battery4> [1. Nonaqueous Electrolyte]

Like ordinary nonaqueous electrolytes, the nonaqueous electrolyte ofinvention 4 includes an electrolyte salt and a nonaqueous solventcontaining the electrolyte salt dissolved therein.

<1-1>Lithium Salt

The lithium salt to be contained in the nonaqueous electrolyte ofinvention 4 is not limited, and known ones for use as electrolyte saltsin a target nonaqueous-electrolyte secondary battery can be employed atwill. Examples of the lithium salt include the same lithium salts asthose enumerated above as examples of the electrolyte salt in invention1.

In the case of using a combination of lithium salts, the kinds of theelectrolytes and the proportions of the lithium salts are the same asthose described above with regard to the electrolyte salt of nonaqueouselectrolyte 1.

Furthermore, the lithium salt concentration, preferred concentration,and the like in the final composition of nonaqueous electrolyte 4 ofinvention 4 are the same as those described above with regard tononaqueous electrolyte 1. The phenomena which occur when theconcentration is outside the range also are the same as those describedabove with regard to nonaqueous electrolyte 1.

Especially in the case where the nonaqueous solvent of the nonaqueouselectrolyte consists mainly of one or more carbonate compounds such asalkylene carbonates or dialkyl carbonates, preferred electrolytes andthe proportion thereof are also the same as those described above withregard to nonaqueous electrolyte 1. The phenomena which occur when theproportion is outside the range also are the same as those describedabove with regard to nonaqueous electrolyte 1.

<1-2. Nonaqueous Solvent>

The nonaqueous solvent contained in the nonaqueous electrolyte ofinvention 4 is the same as that described above with regard to thenonaqueous solvent contained in the nonaqueous electrolyte of invention1.

<1-3> Additives

It is essential that the nonaqueous electrolyte of invention 4 shouldcontain a compound represented by the following general formula (1). Itis preferred that the nonaqueous electrolyte should further contain amonofluorophosphate and/or difluorophosphate. It is also preferred thatthe nonaqueous electrolyte should contain a carbonic acid ester havingat least one of an unsaturated bond and/or a halogen atom. Namely, inembodiment 4-1 of invention 4, the nonaqueous electrolyte contains acompound represented by the following general formula (1) and a“monofluorophosphate and/or difluorophosphate” as additives. Inembodiment 4-2 of invention 4, the nonaqueous electrolyte contains acompound represented by general formula (1) in an amount of from 0.001%by mass to 5% by mass based on the whole nonaqueous electrolyte andfurther contains a “carbonic acid ester having at least one of anunsaturated bond and a halogen atom” in an amount of from 0.001% by massto 5% by mass based on the whole nonaqueous electrolyte.

<1-3-1> Compound Represented by General Formula (3)

The nonaqueous electrolyte of invention 4, either in embodiment 4-1 orin embodiment 4-2, contains a compound represented by the followinggeneral formula (3) in invention 4 as an essential component.

[In general formula (3), A and B each represent any of varioussubstituents, provided that at least one thereof is fluorine; and n is anatural number of 3 or larger.]

In general formula (3) in invention 4, A and B each represents any ofvarious substituents, provided that at least one thereof is fluorine.Although the substituents other than fluorine are not particularlylimited, unsubstituted or fluorine-substituted alkyl or aryl groups arepreferred because of the reactivity thereof. It is also preferred thatsuch an alkyl or aryl group should be bonded to the P through an oxygenatom interposed there between, i.e., through an ether bond. Namely, suchalkyl or aryl groups to which an oxygen atom has been bonded are alsopreferred.

The number of carbon atoms of the alkyl and aryl groups is notparticularly limited. However, in case where the structural or massproportion of the substituents to the basic framework represented bygeneral formula (3) increases, the effect of the addition of thecompound represented by general formula (3) is lessened for the amountthereof and there is a fear about side effects. Because of this, thesubstituents other than fluorine preferably are alkyl or aryl groupshaving preferably 10 or less carbon atoms, more preferably 6 or lesscarbon atoms. With respect to the alkyl groups only, the number ofcarbon atoms thereof is even more preferably 3 or smaller.

Examples of the alkyl groups include methyl, fluoromethyl,difluoromethyl, trifluoromethyl, ethyl, 1-fluoroethyl, 2-fluoroethyl,1,1-difluoroethyl, 1,2-difluoroethyl, 2,2-difluoroethyl,1,1,2-trifluoroethyl, 1,2,2-trifluoroethyl, 2,2,2-trifluoroethyl,1,1,2,2-tetrafluoroethyl, 1,2,2,2-tetrafluoroethyl, pentafluoroethyl,propyl(n-propyl), 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl,1,1-difluoropropyl, 1,2-difluoropropyl, 1,3-difluoropropyl,2,2-difluoropropyl, 2,3-difluoropropyl, 3,3-difluoropropyl,1,1,2-trifluoropropyl, 1,2,2-trifluoropropyl, 1,1,3-trifluoropropyl,1,2,3-trifluoropropyl, 1,3,3-trifluoropropyl, 2,2,3-trifluoropropyl,2,3,3-trifluoropropyl, 3,3,3-trifluoropropyl, 1,1,2,2-tetrafluoropropyl,1,1,2,3-tetrafluoropropyl, 1,1,3,3-tetrafluoropropyl,1,2,2,3-tetrafluoropropyl, 1,2,3,3-tetrafluoropropyl,2,2,3,3-tetrafluoropropyl, 2,3,3,3-tetrafluoropropyl,1,1,2,2,3-pentafluoropropyl, 1,2,2,3,3-pentafluoropropyl,1,1,3,3,3-pentafluoropropyl, 1,2,3,3,3-pentafluoropropyl,2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3-hexafluoropropyl,1,1,2,3,3,3-hexafluoropropyl, 1,2,2,3,3,3-hexafluoropropyl,heptafluoropropyl, 1-methylethyl(isopropyl), 1-fluoro-1-methylethyl,2-fluoro-1-methylethyl, 1,2-difluoro-1-methyethyl,1,2-difluoro-1-(fluoromethyl)ethyl, 1,2,2-trifluoro-1-methylethyl,2,2,2-trifluoro-1-methylethyl, 2,2-difluoro-1-(fluoromethyl)ethyl,1,2,2,2-tetrafluoro-1-methylethyl,1,2,2-trifluoro-1-(fluoromethyl)ethyl,2,2,2-trifluoro-1-(fluoromethyl)ethyl,2,2-difluoro-1-(difluoromethyl)ethyl,1,2,2,2-tetrafluoro-1-(fluoromethyl)ethyl,1,2,2-trifluoro-1-(difluoromethyl)ethyl,2,2,2-trifluoro-1-(difluoromethyl)ethyl,1,2,2,2-tetrafluoro-1-(difluoromethyl)ethyl,2,2,2-trifluoro-1-(trifluoromethyl)ethyl, and1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl.

More preferred of these, from the standpoint of ease of production, aremethyl, fluoromethyl, trifluoromethyl, ethyl, 2-fluoroethyl,2,2,2-trifluoroethyl, pentafluoroethyl, propyl, 3-fluoropropyl,3,3,3-trifluoropropyl, heptafluoropropyl, 1-methylethyl,1-fluoro-1-methylethyl, 2-fluoro-1-methylethyl,2-fluoro-1-(fluoromethyl)ethyl,2,2,2-trifluoro-1-(trifluoromethyl)ethyl, and1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl. Especially preferred aremethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl, and1-methylethyl.

The aryl groups preferably are unsubstituted or fluorine-substitutedphenyl groups. Examples thereof include phenyl, 2-fluorophenyl,3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl,2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl,3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl,2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl,3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl,2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl, andpentafluorophenyl.

More preferred of these are phenyl, 2-fluorophenyl, 3-fluorophenyl,4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl,2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl,3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl,2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, and3,4,5-trifluorophenyl. Especially preferred is phenyl.

In the n repeating units, the A's may be the same or different. However,it is preferred that the A's should be the same. With respect to the B'salso, it is preferred that the B's in the n repeating units should bethe same although they may be the same or different.

The proportion of fluorine atoms in the A's or B's is not particularlylimited. However, it is preferred that the proportion thereof should behigher from the standpoint of easily producing the effect. Theproportion thereof is preferably ⅓ or higher, more preferably ½ orhigher, especially preferably ⅔ or higher. Most preferred is the casewhere all of the A's and B's are fluorine.

Symbol n must be 3 or larger from the standpoint of the stability of thestructure. However, there is no particular upper limit thereon.

Examples of the compound represented by general formula (3) in invention4 include the following.

In embodiment 4-1, the content of those compounds represented by generalformula (3) according to invention 4 in the nonaqueous electrolyte isnot particularly limited. However, the content thereof is preferably inthe range of from 0.001% by mass to 2% by mass, more preferably in therange of from 0.01% by mass to 1.7% by mass, especially preferably inthe range of from 0.05% by mass to 1.3% by mass, and even morepreferably in the range of from 0.1% by mass to 1% by mass. On the otherhand, the content thereof is preferably in the range of from 0.001% byvolume to 1% by volume, more preferably in the range of from 0.01% byvolume to 0.8% by volume, especially preferably in the range of from0.05% by volume to 0.7% by volume, and even more preferably in the rangeof from 0.1% by volume to 0.5% by volume.

In embodiment 4-2, the content of those compounds represented by generalformula (3) according to invention 4 in the nonaqueous electrolyte mustbe in the range of from 0.001% by mass to 5% by mass, and is morepreferably in the range of from 0.01% by mass to 3% by mass, especiallypreferably in the range of from 0.05% by mass to 2% by mass, and evenmore preferably in the range of from 0.1% by mass to 1% by mass. On theother hand, the content thereof is preferably in the range of from0.001% by volume to 3% by volume, more preferably in the range of from0.01% by volume to 2% by volume, especially preferably in the range offrom 0.05% by volume to 1% by volume, and even more preferably in therange of from 0.1% by volume to 0.5% by volume.

The “% by volume” is calculated based on the room-temperature density ofeach compound represented by general formula (3) according to invention4.

In both embodiment 4-1 and embodiment 4-2, the content of thosecompounds represented by general formula (3) according to invention 4 inthe nonaqueous electrolyte is preferably 0.001% by mass or higher and0.001% by volume or higher, more preferably 0 . 01% by mass or higherand 0 . 01% by volume or higher, especially preferably 0.05% by mass orhigher and 0.05% by volume or higher, and even more preferably 0.1% bymass or higher and 0.1% by volume or higher. The upper limit thereof ispreferably 2% by mass or lower and 1% by volume or lower. When theconcentration of the compounds represented by general formula (3)according to invention 4 is too low, there are cases where the effect ofimproving discharge load performances is difficult to obtain. On theother hand, when the concentration thereof is too high, there are caseswhere a decrease in charge/discharge efficiency results. Incidentally,in the case where two or more compounds represented by general formula(3) according to invention 4 are contained, those values of content meantotal amounts thereof.

<1-4. Monofluorophosphate and Difluorophosphate>

The “monofluorophosphate and/or di fluorophosphate” to be used ininvention 4 is the same as in invention 1. Preferred ranges also are thesame as in invention 1.

<1-4-1. Monofluorophosphoric Acid Metal Salt and Difluorophosphoric AcidMetal Salt>

First, in the case where the monofluorophosphate and difluorophosphatein invention 4 are a salt of one or more monofluorophosphate ions or oneor more difluorophosphate ions with one or more specific metal ions,examples of this salt include the same salts as those enumerated abovewith regard to invention 1.

<1-4-2. Monofluorophosphoric Acid Quaternary Onium Salt andDifluorophosphoric Acid Quaternary Onium Salt>

Next, in the case where the monofluorophosphate and difluorophosphate ininvention 4 are a salt of a monofluorophosphate ion or difluorophosphateion with a quaternary onium, examples of this salt include the samesalts as those enumerated above with regard to invention 1.

<1-4-3. Content, Detection (Derivation of Containment), Technical Range,Etc.>

In the nonaqueous electrolyte of invention 4, one monofluorophosphate ordifluorophosphate only may be used or any desired combination of two ormore monofluorophosphates and/or difluorophosphates may be used in anydesired proportion. However, from the standpoint of efficientlyoperating the nonaqueous-electrolyte secondary battery, it is preferredto use one monofluorophosphate or difluorophosphate.

The molecular weight of the monofluorophosphate or difluorophosphate,processes for producing the salt, proportion of the salt in thenonaqueous electrolyte, etc. are the same as those described above withregard to invention 1.

Furthermore, the time at which a monofluorophosphate ordifluorophosphate is detected (the time at which the salt is contained),the place into which the salt is incorporated first (derivation ofcontainment), means of incorporating the salt, detection places based onwhich the salt is considered to be contained (or have been contained) inthe nonaqueous electrolyte, etc. are also the same as those describedabove with regard to invention 1.

<1-5-1> Specific Carbonic Acid Ester

To add a carbonic acid ester having at least one of an unsaturated bondand a halogen atom (hereinafter sometimes referred to as “specificcarbonic acid ester”) as an additive besides the compound represented bygeneral formula (1) in invention 4 and besides the monofluorophosphateor difluorophosphate is preferred in embodiment 4-1 and essential inembodiment 4-2. The incorporation of the specific carbonic acid esterhas the effect of preventing overcharge. In addition, capacityretention, cycle performances, etc. after high-temperature storage canbe improved thereby.

The specific carbonic acid ester may have one or more unsaturated bondsonly or have one or more halogen atoms only, or may have both one ormore unsaturated bonds and one or more halogen atoms.

With respect to this specific carbonic acid ester, the same statementmade hereinabove on the specific carbonate in invention 1 holds.

<1-5-2> Other Additives

The nonaqueous electrolyte of invention 4 may further contain “otheradditives”, such as, e.g., an overcharge inhibitor and an aid forimproving capacity retention and cycle performance afterhigh-temperature storage, so long as these additives do not considerablylessen the effects of invention 4. As such other additives,conventionally known additives can be used at will. Examples of theovercharge inhibitor and the concentration, effect, etc. thereof are thesame as those described above with regard to invention 1.

One of those overcharge inhibitors may be used alone, or any desiredcombination of two or more thereof may be used in any desiredproportion. In the case of employing any desired combination, compoundsin the same class among those enumerated above may be used incombination or compounds in different classes may be used incombination.

Examples of the case where compounds in different classes are used incombination are the same as those enumerated above with regard toinvention 1.

On the other hand, examples of the aid for improving capacity retentionand cycle performances after high-temperature storage include thefollowing phosphorus-containing compounds besides the compoundsenumerated above with regard to invention 1:

-   phosphoric acid esters such as trimethyl phosphate, triethyl    phosphate, and triphenyl phosphate;-   phosphorous acid esters such as trimethyl phosphite, triethyl    phosphite, and triphenyl phosphite; and-   phosphine oxides such as trimethylphosphine oxide, triethylphosphine    oxide, and triphenylphosphine oxide.

The amount of those “other additives” to be incorporated into thenonaqueous electrolyte of invention 4 is not limited, and may be anydesired value unless the effects of invention 4 are considerablylessened thereby. It is, however, desirable to incorporate the additivesin a concentration which is generally 0.01% by mass or higher,preferably 0.1% by mass or higher, more preferably 0.3% by mass orhigher, and is generally 10% by mass or lower, preferably 5% by mass orlower, more preferably 3% by mass or lower, even more preferably 2% bymass or lower, based on the nonaqueous electrolyte of invention 4.

<1-6. Process for Producing Nonaqueous Electrolyte>

For producing the nonaqueous electrolyte of invention 4, the sameprocess as in invention 1 can be used.

[2. Nonaqueous-Electrolyte Secondary Battery]

The nonaqueous-electrolyte secondary battery of invention 4 includes: anegative electrode and a positive electrode which are capable ofoccluding and releasing ions; and the nonaqueous electrolyte ofinvention 4 described above.

The following are the same as those described above with regard toinvention 1: battery constitution; negative electrode; carbonaceousmaterial; constitution and properties of carbonaceous negative electrodeand method of preparation thereof; metal compound material, constitutionand properties of negative electrode employing metal compound material,and method of preparation thereof; positive electrode; separator;battery design; and the like.

By optimizing the structure described above, internal resistance can beminimized. In batteries to be used at a heavy current, it is preferredthat the impedance thereof as measured by the 10-kHz alternating-currentmethod (hereinafter referred to as “direct-current resistancecomponent”) should be regulated to 10 milliohms (mΩ) or lower. It ismore preferred to regulate the direct-current resistance componentthereof to 5 milliohms (mΩ) or lower.

When the direct-current resistance component is reduced to 0.1 milliohmor lower, high-output performances improve. However, this regulationresults in an increased proportion of current collector structurematerials and may reduce the battery capacity.

The nonaqueous electrolyte of invention 4 is effective in reducing theresistance of reactions relating to lithium elimination from andinsertion into electrode active materials. This is a factor whichrenders satisfactory low-temperature discharge performances possible.However, in ordinary batteries having a direct-current resistance higherthan 10 milliohms (mΩ), there are cases where the effect of reducingreaction resistance cannot be 100% reflected in low-temperaturedischarge performances because of inhibition by the direct-currentresistance. By using a battery having a low direct-current resistancecomponent, that problem can be mitigated and the effect of thenonaqueous electrolyte of invention 4 can be fully produced.

It is especially preferred that this requirement and the above-describedrequirement that the battery elements to be held in one battery case ofa secondary battery have an electric capacity (electric capacitymeasured when the battery in a fully charged state is discharged to adischarged state) of 3 ampere-hour (Ah) or higher should besimultaneously satisfied from the standpoints of enabling the nonaqueouselectrolyte to produce its effect and fabricating a battery having highlow-temperature discharge performances.

<Nonaqueous Electrolyte 5 and Nonaqueous-Electrolyte Secondary Battery5> [1. Nonaqueous Electrolyte]

Like ordinary nonaqueous electrolytes, the nonaqueous electrolyte ofinvention 5 includes a lithium salt and an ambient-temperature-moltensalt containing the lithium salt dissolved therein. Usually, the lithiumsalt and the molten salt are contained as main components.

<1-1> Lithium Salt

The lithium salt to be contained in the nonaqueous electrolyte ofinvention 5 is not limited, and known ones for use as electrolytes in atarget nonaqueous-electrolyte secondary battery can be employed at will.Examples of the lithium salt include the same lithium salts as thoseenumerated above as examples of the electrolyte in invention 1.

In the case of using a combination of lithium salts, the kinds of theelectrolytes and the proportions of the lithium salts are the same asthose described above with regard to the electrolyte of nonaqueouselectrolyte 1.

The concentration of the lithium salt in the nonaqueous electrolyte isnot particularly limited. However, the concentration thereof isgenerally 0.1 mol/L or higher, preferably 0.2 mol/L or higher, morepreferably 0.3 mol/L or higher. The upper limit thereof is generally 3mol/L or lower, preferably 2 mol/L or lower, more preferably 1.8 mol/Lor lower, especially preferably 1.5 mol/L or lower. When theconcentration of the lithium salt is too low, there are cases where thisnonaqueous electrolyte has insufficient electrical conductivity. On theother hand, when the concentration thereof is too high, there are caseswhere an increase in viscosity results and this reduces electricalconductivity. There are also cases where battery performances decrease.

The nonaqueous electrolyte of invention 5 includes a lithium salt and anambient-temperature-molten salt. This nonaqueous electrolyte contains“at least one compound selected from the group consisting ofmonofluorophosphates and difluorophosphates”.

<1-2. Ambient-Temperature-Molten Salt>

The term “ambient-temperature-molten salt” in invention 5 means an ionicsubstance (salt) which has a molecular structure constituted of one ormore cations and one or more anions and which is partly or wholly liquidat 45° C. Even a compound having a melting point of 45° C. or higher inthermal analysis falls under the category of ambient-temperature-moltensalts according to invention 5 when the compound can be caused, by rapidcooling or the like, to stably retain a supercooled state at 45° C. overlong and exist as a liquid. Furthermore, even a salt which is in a solidstate at 45° C. falls under the category of ambient-temperature-moltensalts according to invention 5 in the case where this salt, when mixedwith one or more other ionic substances, such as a lithium salt and amonofluorophosphate or difluorophosphate, gives a mixture which is in aliquid state at 45° C.

The ambient-temperature-molten salt to be used in invention 5 is notparticularly limited so long as the salt satisfies the requirement shownabove. Of such ambient-temperature-molten salts, ones which are in aliquid state at 25° C. are preferred and ones which are in a liquidstate at 15° C. are more preferred. Especially preferred are ones whichare in a liquid state at 10° C.

The cation structure as a component of the ambient-temperature-moltensalt is not particularly limited. However, a cation structure formedfrom an organic substance is preferred because the salt having thisstructure is apt to be in a liquid state at 45° C. It is more preferred,from the standpoint of attaining a low coefficient of viscosity, thatthe nonaqueous electrolyte should contain at least oneambient-temperature-molten salt selected from the group consisting oftertiary sulfonium salts having a structure represented by the followinggeneral formula (6), quaternary ammonium salts having a structurerepresented by the following general formula (7), and quaternaryphosphonium salts having a structure represented by the followinggeneral formula (8).

[In general formula (6), R_(1r), R_(2r), and R_(3r) each independentlyrepresent an organic group having 1-12 carbon atoms, provided that twoorganic groups of the R_(1r), R_(2r), and R_(3r) may have been bonded toeach other to form a ring structure.]

[In general formula (7) , R_(4r), R_(5r), R_(6r), and R_(7r) eachindependently represent an organic group having 1-12 carbon atoms,provided that two to the four organic groups of the R_(4r), R_(5r),R_(6r), and R_(7r) may have been bonded to each other to form a ringstructure and that two organic groups of the R_(4r), R_(5r), R_(6r), andR_(7r) may actually be one organic group bonded to the “N” atom througha double bond.]

[In general formula (8), R_(8r), R_(9r), R_(10r), and R_(11r) eachindependently represent an organic group having 1-12 carbon atoms,provided that two to the four organic groups of the R_(8r), R_(9r),R_(10r), and R_(11r) may have been bonded to each other to form a ringstructure and that two organic groups of the R_(8r), R_(9r), R_(10r),and R_(11r) may actually be one organic group bonded to the “P⁺” atomthrough a double bond.]

[Compounds Represented by General Formula (6)]

R_(1r), R_(2r), and R_(3r) in the sulfonium cation structure representedby general formula (6) in invention 5 are organic groups which each have1-12 carbon atoms and which may be the same or different. Examples ofR_(1r), R_(2r), and R_(3r) include chain alkyl groups such as methyl,ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, and t-butyl;cycloalkyl groups such as cyclohexyl and norbornanyl; alkenyl groupssuch as vinyl, 1-propenyl, allyl, butenyl, and 1,3-butadienyl; alkynylgroups such as ethynyl, propynyl, and butynyl; halogenated alkyl groupssuch as trifluoromethyl, trifluoroethyl, and hexafluoropropyl; arylgroups such as phenyl which may have one or more substituents, e.g.,alkyl substituents; aralkyl groups such as benzyl and phenylethyl;trialkylsilyl groups such as trimethylsilyl; carbonyl-containing alkylgroups such as ethoxycarbonylethyl; alkyl groups containing one or moreether groups, such as methoxyethyl, phenoxymethyl, ethoxyethyl,allyloxyethyl, methoxyethoxyethyl, and ethoxyethoxyethyl; andsulfonyl-containing alkyl groups such as sulfonylmethyl.

It is, however, noted that R_(1r), R_(2r), and R_(3r) in the sulfoniumcation structure may have been bonded to each other to form a ringstructure, and that besides the substituents shown above, a substituentmay have been bonded to the R_(1r), R_(2r), and R_(3r) through asaturated or unsaturated bond involving a heteroatom such as, e.g.,oxygen, nitrogen, sulfur, or phosphorus.

Preferred of those R_(1r), R_(2r), and R_(3r) are alkyl groups having1-6 carbon atoms, halogenated alkyl groups, aryl groups, and alkylgroups having one or more ether groups. This is because these groupsserve to reduce the intermolecular interaction of the sulfonium salt andare generally apt to thereby impart a low melting point to the salt.

Especially preferred of such sulfonium structures are the followingbecause the following sulfoniums are apt to bring about a lowcoefficient of viscosity: trimethylsulfonium, triethylsulfonium,dimethylethylsulfonium, methyldiethylsulfonium, tripropylsulfonium,dimethylpropylsulfonium, methyldipropylsulfonium,diethylpropylsulfonium, ethyldipropylsulfonium,methylethylpropylsulfonium, tributylsulfonium, dimethylbutylsulfonium,methyldibutylsulfonium, diethylbutylsulfonium, ethyldibutylsulfonium,dipropylbutylsulfonium, propyldibutylsulfonium,methylethylbutylsulfonium, methylpropylbutylsulfonium,ethylpropylbutylsulfonium, compounds formed by replacing one or more ofthe hydrogen atoms of the alkyl groups of each of these sulfoniums withfluorine atoms, dimethylvinylsulfonium, dimethylallylsulfonium,dimethylbutenylsulfonium, diethylvinylsulfonium, diethylallylsulfonium,diethylbutenylsulfonium, methylethylvinylsulfonium,methylethylallylsulfonium, methylethylbutenylsulfonium,dimethylmethoxymethylsulfonium, dimethylmethoxyethylsulfonium,dimethylethoxymethylsulfonium, dimethylethoxyethylsulfonium,dimethylmethoxyethoxyethylsulfonium, dimethylethoxyethoxyethylsulfonium,diethylmethoxymethylsulfonium, diethylmethoxyethylsulfonium,diethylethoxyethylsulfonium, diethylmethoxyethoxyethylsulfonium,diethylethoxyethoxyethylsulfonium, and the like.

The anion of the tertiary sulfonium salts having a structure representedby general formula (6) in invention 5 is not particularly limited.However, anions having a van der Waals radius of 50 Å or larger arepreferred because the salt having such an anion is apt to be in a liquidstate at 45° C. or lower. More preferred of these are anion structuresconstituted of an element formally having a negative charge and one ormore electron-withdrawing substituents bonded thereto. This is becausethe salt having such an anion structure is apt to be in a liquid stateat room temperature.

Especially preferred of such anion structures are ones in which theelectron-withdrawing substituents are any of the following: a fluorineatom; a cyano group; a carbonyl group having fluorine or a cyano, alkyl,fluoroalkyl, cyanoalkyl, phenyl, fluorophenyl, or cyanophenyl group, anda carboxyl group, sulfo group, and sulfonyl group; a phenyl group, afluorophenyl group, a phenyl group having a fluoroalkyl group, and acyanophenyl group; a phenoxy group, a fluorophenoxy group, a phenylgroup having a fluoroalkyl group, and a cyanophenoxy group; athiophenoxy group, a fluorothiophenoxy group, a thiophenoxy group havinga fluoroalkyl group, and a cyanothiophenoxy group; a fluoroalkoxy groupand a cyanoalkoxy group; and a fluorothioalkoxy group and acyanothioalkoxy group. This is because these anion structures haveexcellent heat resistance and excellent oxidation resistance.

Furthermore, Lewis-acid compounds such as BF₃, AlF₃, PF₃, PF_(S), SbF₅,and AsF₅ can be included in especially preferred substituents like theelectron-withdrawing substituents shown above, because these Lewis-acidcompounds also interact with the negatively charged site in the anionstructure to thereby increase electrochemical oxidation stability of theanion.

Of those anions, the following are exceedingly preferred because thefollowing anions have a satisfactory balance among ionic conductivity,viscosity coefficient, stability to oxidation/reduction,charge/discharge efficiency, high-temperature storability, etc. inapplication to nonaqueous-electrolyte secondary batteries: inorganicanions such as BF₄ ⁻, AlF₄ ⁻, ClO₄ ⁻, PF₆ ⁻, SbF₆ ⁻, SiF₆ ²⁻, AsF₆ ⁻,WF₇ ⁻, CO₃ ²⁻, FSO₃ , (FSO₂)₂N⁻, (FSO₂)₃C⁻, NO₃ ⁻, FO₄ ³⁻, PO₃F⁻, PO₂F₂⁻, and B₁₂F₁₂ ²⁻; organic anions such as (CN)₂N⁻, (CNCO)₂N⁻, (CNSO₂)₂N⁻,(CF₃CO)₂N⁻, (CF₃CF₂CO)₂N⁻, (CF₃SO₂)₂N⁻, (CF₃CO)(CF₃SO₂)N⁻,(CF₃SO₂)(CF₃CF₂SO₂)N⁻, (CF₃CF₂SO₂)₂N⁻, (CF₃SO₂)(C₄F₉SO₂)N⁻, cyclic1,2-perfluoroethanedisulfonylimide, cyclic1,3-perfluoropropanedisulfonylimide, (CN)₃C⁻, (CNCO)₃C⁻, (CNSO₂)₃C⁻,(FSO₂)₃C⁻, (CF₃CO)₃C⁻, (CF₃CF₂CO)₃C⁻, (CH₃SO₂)₃C⁻, CF₃BF₃ ⁻, CF₃CF₂BF₃⁻, CF₃CF₂CF₂BF₃ ⁻, (CF₃CO)BF₃, (CF₃SO₂)BF₃ ⁻, (CF₃CF₂SO₂)BF₃ ⁻,(CF₃)₂BF₂ ⁻, (CF₃CF₂)₂BF₂ ⁻, (CF₃SO₂)₂BF₂ ⁻, (CF₃CF₂SO₂)₂BF₂ ⁻,(CF₃)₂BF⁻, (CF₃CF₂)₃BF⁻, (CF₃CO)₃BF⁻, (CF₃SO₂)₃BF⁻, (CF₃CF₂SO₂)₃BF⁻,(CF₃)₄B⁻, (CF₃CF₂)₄B⁻, (C₆F₅)₄B⁻, (CF₃CO₂)₄B⁻, (CF₃SO₃)₄B⁻,(CF₃CF₂SO₃)₄B⁻, (CF₃)₃CO)₄B⁻, ((CF₃)₂CHO)₄B⁻, (Ph(CF₃)₂CO)₄B⁻,(C₆F₅O)₄B⁻, (CF₃CO)₄Al⁻, (CF₃SO₂)₄Al⁻, CF₃CF₂SO₂)₄Al⁻, ((CF₃)₃CO)₄Al⁻,(CF₃)₂CHO)₄Al⁻, (Ph(CF₃)₂CO)₄Al⁻, (C₆F₅O)₄Al⁻, (CF₃)₂PF₄ ⁻, (C₂F₅)₂PF⁻,(CF₃SO₂)₂PF₄ ⁻, (C₂F₅SO₂)₂PF₄ ⁻, (CF₃)₃PF₃ ⁻, (C₂F₅)₃PF₃ ⁻, (CF₃SO₂)₃PF₃⁻, (C₂F₅SO₂)₃PF₃ ⁻, (CF₃)₄PF₂ ⁻, (C₂F₅)₄PF₂ ⁻, (CF₃SO₂)₄PF₂ ⁻, and(C₂F₅SO₂)₄PF₂ ⁻; and dicarboxylic-acid-containing complex anions such asbis(oxalato)borate, tris(oxalato)phosphate, and difluorooxalatoborate.

[Compounds Represented by General Formula (7)]

R_(4r), R_(5r), R_(6r), and R_(7r) in the quaternary ammonium cationstructure represented by general formula (7) in invention 5 are organicgroups which each have 1-12 carbon atoms and which may be the same ordifferent. Examples of R_(4r), R_(5r), R_(6r), and R_(7r) include thesame organic groups as those enumerated above with regard to the“R_(1r), R_(2r), and R_(3r)” in general formula (1), i.e., chain alkylgroups, cycloalkyl groups, alkenyl groups, alkynyl groups, halogenatedalkyl groups, aryl groups such as phenyl which may have one or morealkyl substituents, aralkyl groups, trialkylsilyl groups,carbonyl-containing alkyl groups, alkyl groups containing one or moreether groups, and sulfonyl-containing alkyl groups. Preferred examplesthereof also are the same as those enumerated above with regard to the“R_(1r), R_(2r), and R_(3r)” in general formula (1).

It is, however, noted that two to the four of the R_(4r), R_(5r),R_(6r), and R_(7r) may have been bonded to each other to form a ringstructure, and that besides the substituents shown above, a substituentmay have been bonded to R_(4r), R_(5r), R_(6r), and R_(7r) through asaturated or unsaturated bond involving a heteroatom such as oxygen,nitrogen, sulfur, or phosphorus.

In the case where the quaternary ammonium cation structure representedby general formula (7) given above is a chain ammonium cation, it ispreferred that R_(4r), R_(5r), R_(6r), and R_(7r) each should be analkyl group having 1-6 carbon atoms, a halogenated alkyl group, an allylgroup, or an alkyl group containing one or more ether groups. This isbecause these groups serve to reduce the intermolecular interaction ofthe ammonium salt and are generally apt to thereby impart a low meltingpoint to the salt.

More preferred of such ammonium cation structures are the followingbecause the following ammoniums are apt to bring about a low coefficientof viscosity: trimethylpropylammonium, trimethylbutylammonium,trimethylpentylammonium, trimethylhexylammonium,dimethylethylpropylammonium, dimethylethylbutylammonium,dimethylethylpentylammonium, dimethylethylhexylammonium,dimethyldipropylammonium, dimethylpropylbutylammonium,dimethylpropylpentylammonium, dimethylpropylhexylammonium,dimethyldibutylammonium, dimethylbutylpentylammnium,dimethylbutylhexylammonium, dimethyldipentylammonium,dimethylpentylhexylammonium, dimethyldihexylammonium,methyldiethylpropylammonium, methyldiethylbutylammonium,methyldiethylpentylammonium, methyldiethylhexylammonium,methylethyldipropylammonium, methylethylpropylbutylammonium,methylethylpropylpentylammonium, methylethylpropylhexylammonium,methylethyldibutylammonium, methylethylbutylpentylammonium,methylethylbutylhexylammnium, methylethyldipentylammonium,methylethylpentylhexylammonium, methylethyldihexylammonium,methyltripropylammonium, methyldipropylbutylammonium,methyldipropylpentylammonium, methyldipropylhexylammonium,methylpropyldibutylammonium, methylpropylbutylpentylammonium,methylpropylbutylhexylammonium, methylpropyldipentylammonium,methylpropylpentylhexylammonium, methylpropyldihexylammonium,methyltributylammonium, methyldibutylpentylammonium,methyldibutylhexylammonium, methylbutyldipentylammonium,methylbutylpentylhexylammonium, methylbutyldihexylammonium,methyltripentylammonium, methyldipentylhexylammonium,methylpentyldihexylammonium, methyltrihexylammonium,triethylpropylammonium, triethylbutylammonium, triethylpentylammonium,triethylhexylammonium, compounds formed by replacing one or more of thehydrogen atoms of the alkyl groups of each of these ammoniums withfluorine atoms, trimethylallylammoniuM, trimethylbutenylammonium,trimethylmethoxymethylammonium, trimethylmethoxyethylammonium,trimethylmethoxyethoxyethylammonium, and the like.

Especially preferred of these are trimethylpropylammonium,trimethylbutylammonium, trimethylpentylammonium, trimethylhexylammonium,dimethylethylpropylammonium, dimethylethylbutylammonium,dimethylethylpentylammonium, dimethylethylhexylammonium,dimethylpropylbutylammonium, dimethylpropylpentylammonium,dimethylpropylhexylammonium, triethylpropylammonium,triethylbutylammonium, triethylpentylammonium, triethylhexylammonium,compounds formed by replacing one or more of the hydrogen atoms of thealkyl groups of each of these ammoniums with fluorine atoms,trimethylallylammonium, trimethylbutenylammonium,trimethylmethoxymethylammonium, trimethylmethoxyethylammonium, and thelike. This is because these cations do not have too large a size andenable the ambient-temperature-molten salt to have a moderate number ofions per unit volume (i.e., ion density) so as not to impair thefeatures of the ambient-temperature-molten salt. Namely, these cationsenable the ambient-temperature-molten salt to have an excellent balancebetween melting point and the coefficient of viscosity.

In the quaternary ammonium cation structure represented by generalformula (7), two to the four of the R_(4r), R_(5r), R_(6r), and R_(7r)may have been bonded to each other to form a ring structure. Inparticular, saturated heterocyclic structures represented by thefollowing general formula (9), general formula (10), and general formula(11) are preferred because these saturated heterocyclic structures aregenerally apt to form a salt having a low melting point. In thefollowing general formula (9), general formula (10) , and generalformula (11) , R_(12a), R_(13a), R_(12b), R_(13b), R_(12c), and R_(13c)are the same as the “R_(4r), R_(5r), R_(6r), and R_(7r) which may bedifferent from each other” in general formula (7).

Of the pyrrolidinium cations represented by general formula (9), thefollowing pyrrolidiniums are more preferred because they are generallyapt to form an ambient-temperature-molten salt: dimethylpyrrolidinium,methylethylpyrrolidinium, diethylpyrrolidinium,methylpropylpyrrolidinium, ethylpropylpyrrolidinium,dipropylpyrrolidinium, methylbutylpyrrolidinium,ethylbutylpyrrolidinium, propylbutylpyrrolidinium, dibutylpyrrolidinium,compounds formed by replacing one or more of the hydrogen atoms of thealkyl groups of each of these pyrrolidiniums with fluorine atoms,methylvinylpyrrolidinium, ethylvinylpyrrolidinium,propylvinylpyrrolidinium, butylvinylpyrrolidinium,methylallylpyrrolidinium, ethylallylpyrrolidinium,propylallylpyrrolidinium, butylallylpyrrolidinium, diallylpyrrolidinium,methylbutenylpyrrolidinium, ethylbutenylpyrrolidinium,propylbutenylpyrrolidinium, butylbutenylpyrrolidinium,dibutenylpyrrolidinium, methylmethoxymethylpyrrolidinium,methylmethoxyethylpyrrolidinium, methylethoxyethylpyrrolidinium,methylmethoxyethoxyethylpyrrolidinium,methylethoxyethoxyethylpyrrolidinium, ethylmethoxymethylpyrrolidinium,ethylmethoxyethylpyrrolidinium, ethylethoxyethylpyrrolidinium,ethylmethoxyethoxyethylpyrrolidinium,ethylethoxyethoxyethylpyrrolidinium, propylmethoxymethylpyrrolidinium,propylmethoxyethylpyrrolidinium, propylethoxyethylpyrrolidinium,propylmethoxyethoxyethylpyrrolidinium,propylethoxyethoxyethylpyrrolidinium, butylmethoxymethylpyrrolidinium,butylmethoxyethylpyrrolidinium, butylethoxyethylpyrrolidinium,butylmethoxyethoxyethylpyrrolidinium,butylethoxyethoxyethylpyrrolidinium, and the like.

Especially preferred of these are the following because the followingpyrrolidiniums are apt to bring about a low coefficient of viscosity:methylethylpyrrolidinium, methylpropylpyrrolidinium,ethylpropylpyrrolidinium, methylbutylpyrrolidinium,ethylbutylpyrrolidinium, compounds formed by replacing one or more ofthe hydrogen atoms of the alkyl groups of each of these pyrrolidiniumswith fluorine atoms, methylallylpyrrolidinium, ethylallylpyrrolidinium,propylallylpyrrolidinium, butylallylpyrrolidinium,methylbutenylpyrrolidinium, ethylbutenylpyrrolidinium,propylbutenylpyrrolidinium, butylbutenylpyrrolidinium,methylmethoxymethylpyrrolidinium, methylmethoxyethylpyrrolidinium,ethylmethoxymethylpyrrolidinium, ethylmethoxyethylpyrrolidinium, and thelike.

Of the piperidinium cations represented by general formula (10), thefollowing piperidiniums are more preferred because they are generallyapt to form an ambient-temperature-molten salt: dimethylpiperidinium,methylethylpiperidinium, diethylpiperidinium, methylpropylpiperidinium,ethylpropylpiperidinium, dipropylpiperidinium, methylbutylpiperidinium,ethylbutylpiperidinium, propylbutylpiperidinium, dibutylpiperidinium,compounds formed by replacing one or more of the hydrogen atoms of thealkyl groups of each of these piperidiniums with fluorine atoms,methylvinylpiperidinium, ethylvinylpiperidinium,propylvinylpiperidinium, butylvinylpiperidinium,methylallylpiperidinium, ethylallylpiperidinium,propylallylpiperidinium, butylallylpiperidinium, diallylpiperidinium,methylbutenylpiperidinium, ethylbutenylpiperidinium,propylbutenylpiperidinium, butylbutenylpiperidinium,dibutenylpiperidinium, methylmethoxymethylpiperidinium,methylmethoxyethylpiperidinium, methylethoxyethylpiperidinium,methylmethoxyethoxyethylpiperidinium,methylethoxyethoxyethylpiperidinium, ethylmethoxymethylpiperidinium,ethylmethoxyethylpiperidinium, ethylethoxyethylpiperidinium,ethylmethoxyethoxyethylpiperidinium, ethylethoxyethoxyethylpiperidinium,propylmethoxymethylpiperidinium, propylmethoxyethylpiperidinium,propylethoxyethylpiperidinium, propylmethoxyethoxyethylpiperidinium,propylethoxyethoxyethylpiperidinium, butylmethoxymethylpiperidinium,butylmethoxyethylpiperidinium, butylethoxyethylpiperidinium,butylmethoxyethoxyethylpiperidinium, butylethoxyethoxyethylpiperidinium,and the like.

Especially preferred of these are the following because the followingpiperidiniums are apt to bring about a low coefficient of viscosity:methylethylpiperidinium, methylpropylpiperidinium,ethylpropylpiperidinium, methylbutylpiperidinium,ethylbutylpiperidinium, compounds formed by replacing one or more of thehydrogen atoms of the alkyl groups of each of these piperidiniums withfluorine atoms, methylallylpiperidinium, ethylallylpiperidinium,propylallylpiperidinium, butylallylpiperidinium,methylbutenylpiperidinium, ethylbutenylpiperidinium,propylbutenylpiperidinium, butylbutenylpiperidinium,methylmethoxymethylpiperidinium, methylmethoxyethylpiperidinium,ethylmethoxymethylpiperidinium, ethylmethoxyethylpiperidinium, and thelike.

Of the morpholinium cations represented by general formula (11), thefollowing morpholiniums are more preferred because they are generallyapt to form an ambient-temperature-molten salt: dimethylmorpholinium,methylethylmorpholinium, diethylmorpholinium, methylpropylmorpholinium,ethylpropylmorpholinium, dipropylmorpholinium, methylbutylmorpholinium,ethylbutylmorpholinium, propylbutylmorpholinium, dibutylmorpholinium,compounds formed by replacing one or more of the hydrogen atoms of thealkyl groups of each of these morpholiniums with fluorine atoms,methylvinylmorpholinium, ethylvinylmorpholinium,propylvinylmorpholinium, butylvinylmorpholinium,methylallylmorpholinium, ethylallylmorpholinium,propylallylmorpholinium, butylallylmorpholinium, diallylmorpholinium,methylbutenylmorpholinium, ethylbutenylmorpholinium,propylbutenylmorpholinium, butylbutenylmorpholinium,dibutenylmorpholinium, methylmethoxymethylmorpholinium,methylmethoxyethylmorpholinium, methylethoxyethylmorpholinium,methylmethoxyethoxyethylmorpholinium,methylethoxyethoxyethylmorpholinium, ethylmethoxymethylmorpholinium,ethylmethoxyethylmorpholinium, ethylethoxyethylmorpholinium,ethylmethoxyethoxyethylmorpholinium, ethylethoxyethoxyethylmorpholinium,propylmethoxymethylmorpholinium, propylmethoxyethylmorpholinium,propylethoxyethylmorpholinium, propylmethoxyethoxyethylmorpholinium,propylethoxyethoxyethylmorpholinium, butylmethoxymethylmorpholinium,butylmethoxyethylmorpholinium, butylethoxyethylmorpholinium,butylmethoxyethoxyethylmorpholinium, butylethoxyethoxyethylmorpholinium,and the like.

Especially preferred of these are the following because the followingmorpholiniums are apt to bring about a low coefficient of viscosity:methylethylmorpholinium, methylpropylmorpholinium,ethylpropylmorpholinium, methylbutylmorpholinium,ethylbutylmorpholinium, compounds formed by replacing one or more of thehydrogen atoms of the alkyl groups of each of these morpholiniums withfluorine atoms, methylallylmorpholinium, ethylallylmorpholinium,propylallylmorpholinium, butylallylmorpholinium,methylbutenylmorpholinium, ethylbutenylmorpholinium,propylbutenylmorpholinium, butylbutenylmorpholinium,methylmethoxymethylmorpholinium, methylmethoxyethylmorpholinium,ethylmethoxymethylmorpholinium, ethylmethoxyethylmorpholinium, and thelike.

A quaternary ammonium cation structure represented by general formula(7) in which two organic groups of the R_(4r), R_(5r), R_(6r), andR_(7r) actually are one organic group and this one organic group hasbeen bonded to the “N⁺” atom through a double bond is also included ingeneral formula (7) in invention 5. Namely, the case where two of theR_(4r), R_(5r), R_(6r), and R_(7r) have been united with each other toform an alkylidene group is also included in general formula (7) . Suchstructures in which the alkylidene group forms a ring structure are alsopreferred. Of these structures, the unsaturated heterocyclic structuresshown below are preferred because the following structures are generallyapt to form a salt having a low melting point.

Of the pyridinium cations represented by general formula (12), thefollowing are preferred because the following cations are generally aptto form an ambient-temperature-molten salt. Preferred pyridinium cationsare ones in which R₁₄ is any of ethyl, propyl, butyl, pentyl, and hexylgroups, compounds formed by replacing one or more of the hydrogen atomsof each of these alkyl groups with fluorine atoms, allyl, butenyl,methoxymethyl, methoxyethyl, ethoxyethyl, methoxyethoxyethyl, andethoxyethoxyethyl groups, and the like, and R₁₅ to R₁₉ each are ahydrogen atom or methyl.

Especially preferred of these are the following because the followingpyridiniums are apt to bring about a low coefficient of viscosity:1-ethylpyridinium, 1-propylpyridinium, 1-butylpyridinium,1-pentylpyridinium, 1-hexylpyridinium, 1-allylpyridinium,1-butenylpyridinium, 1-methoxymethylpyridinium,1-methoxyethylpyridinium, and the like.

Of the pyridazinium cations represented by general formula (13), thefollowing are preferred because the following cations are generally aptto form an ambient-temperature-molten salt. Preferred pyridaziniumcations are ones in which R₂₀ is any of ethyl, propyl, butyl, pentyl,andhexyl groups, compounds formed by replacing one or more of thehydrogen atoms of each of these alkyl groups with fluorine atoms, allyl,butenyl, methoxymethyl, methoxyethyl, ethoxyethyl, methoxyethoxyethyl,and ethoxyethoxyethyl groups, and the like, and R₂₁ to R₂₄ each are ahydrogen atom or methyl.

Especially preferred of these are the following because the followingpyridaziniums are apt to bring about a low coefficient of viscosity:1-ethylpyridazinium, 1-propylpyridazinium, 1-butylpyridazinium,1-pentylpyridazinium, 1-hexylpyridazinium, 1-allylpyridazinium,1-butenylpyridazinium, 1-methoxymethylpyridazinium,1-methoxyethylpyridazinium, and the like.

Of the pyrimidinium cations represented by general formula (14), thefollowing are preferred because the following cations are generally aptto form an ambient-temperature-molten salt. Preferred pyrimidiniumcations are ones in which R₂₅ is any of ethyl, propyl, butyl, pentyl,and hexyl groups, compounds formed by replacing one or more of thehydrogen atoms of each of these alkyl groups with fluorine atoms, allyl,butenyl, methoxymethyl, methoxyethyl, ethoxyethyl, methoxyethoxyethyl,and ethoxyethoxyethyl groups, and the like, and R₂₆ to R₂₉ each are ahydrogen atom or methyl.

Especially preferred of these are the following because the followingpyrimidiniums are apt to bring about a low coefficient of viscosity:1-ethylpyrimidinium, 1-propylpyrimidinium, 1-butylpyrimidinium,1-pentylpyrimidinium, 1-hexylpyrimidinium, 1-allylpyrimidinium,1-butenylpyrimidinium, 1-methoxymethylpyrimidinium,1-methoxyethylpyrimidinium, and the like.

Of the pyrazinium cations represented by general formula (15), thefollowing are preferred because the following cations are generally aptto form an ambient-temperature-molten salt. Preferred pyrazinium cationsare ones in which R₃₀ is any of ethyl, propyl, butyl, pentyl, and hexylgroups, compounds formed by replacing one or more of the hydrogen atomsof each of these alkyl groups with fluorine atoms, allyl, butenyl,methoxymethyl, methoxyethyl, ethoxyethyl, methoxyethoxyethyl, andethoxyethoxyethyl groups, and the like, and R₃₁ to R₃₄ each are ahydrogen atom or methyl.

Especially preferred of these are the following because the followingpyraziniums are apt to bring about a low coefficient of viscosity:1-ethylpyrazinium, 1-propylpyrazinium, 1-butylpyrazinium,1-pentylpyrazinium, 1-hexylpyrazinium, 1-allylpyrazinium,1-butenylpyrazinium, 1-methoxymethylpyrazinium,1-methoxyethylpyrazinium, and the like.

Of the imidazolium cations represented by general formula (16), thefollowing are preferred because the following cations are generally aptto form an ambient-temperature-molten salt. Preferred imidazoliumcations are ones in which R₃₆ and R₃₉ each are any of ethyl, propyl,butyl, pentyl, and hexyl groups, compounds formed by replacing one ormore of the hydrogen atoms of each of these alkyl groups with fluorineatoms, vinyl, allyl, butenyl, methoxymethyl, methoxyethyl, ethoxyethyl,methoxyethoxyethyl, and ethoxyethoxyethyl groups, and the like, and R₃₅,R₃₇, and R₃₈ each are a hydrogen atom or methyl.

Especially preferred of these are the following because the followingimidazoliums are apt to bring about a low coefficient of viscosity:1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium,1-propyl-3-methylimidazolium, 1-butyl-3-methylimidazolium,1-pentyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium,1,3-diethylimidazolium, 1-ethyl-3-propylimidazolium,1-ethyl-3-butylimidazolium, 1-ethyl-3-pentylimidazolium,1-ethyl-3-hexylimidazolium, 1,3-dipropylimidazolium,1-propyl-3-butylimidazolium, 1-propyl-3-pentylimidazolium,1-hexyl-3-butylimidazolium, 1,2,3-trimethylimidazolium,1-ethyl-2,3-dimethylimidazolium, 1-propyl-2,3-dimethylimidazolium,1-butyl-2,3-dimethylimidazolium, 1-pentyl-2,3-dimethylimidazolium,1-hexyl-2,3-dimethylimidazolium, 1,3-diethyl-2-methylimidazolium,1-propyl-2-methyl-3-ethylimidazolium,1-butyl-2-methyl-3-ethylimidazolium,1-pentyl-2-methyl-3-ethylimidazolium,1-hexyl-2-methyl-3-ethylimidazolium, 1,2,3,4,5-hexamethylimidazolium,1-ethyl-2,3,4,5-tetramethylimidazolium,1-propyl-2,3,4,5-tetramethylimidazolium,1-butyl-2,3,4,5-tetramethylimidazolium,1-pentyl-2,3,4,5-tetramethylimidazolium,1-hexyl-2,3,4,5-tetramethylimidazolium, compounds formed by replacingone or more of the hydrogen atoms of the alkyl groups of each of theseimidazoliums with fluorine atoms, 1-allyl-3-methylimidazolium,1-allyl-3-ethylimidazolium, 1-allyl-3-propylimidazolium,1-allyl-3-butylimidazolium, 1-allyl-2,3-dimethylimidazolium,1-allyl-2,3,4,5-tetramethylimidazolium, 1-butenyl-3-methylimidazolium,1-butenyl-3-ethylimidazolium, 1-butenyl-3-propylimidazolium,1-butenyl-3-butylimidazolium, 1-butenyl-2,3-dimethylimidazolium,1-butenyl-2,3,4,5-tetramethylimidazolium,1-methoxymethyl-3-methylimidazolium, 1-methoxymethyl-3-ethylimidazolium,1-methoxymethyl-3-propylimidazolium, 1-methoxymethyl-3-butylimidazolium,1-methoxymethyl-2,3-dimethylimidazolium,1-methoxymethyl-2,3,4,5-tetramethylimidazolium,1-methoxyethyl-3-methylimidazolium, 1-methoxyethyl-3-ethylimidazolium,1-methoxyethyl-3-propylimidazolium, 1-methoxyethyl-3-butylimidazolium,1-methoxyethyl-2,3-dimethylimidazolium,1-methoxyethyl-2,3,4,5-tetramethylimidazolium, and the like.

Of the oxazolium cations represented by general formula (17), thefollowing are preferred because the following cations are generally aptto form an ambient-temperature-molten salt. Preferred oxazolium cationsare ones in which R₄₁ is any of ethyl, propyl, butyl, pentyl, and hexylgroups, compounds formed by replacing one or more of the hydrogen atomsof each of these alkyl groups with fluorine atoms, vinyl, allyl,butenyl, methoxymethyl, methoxyethyl, ethoxyethyl, methoxyethoxyethyl,and ethoxyethoxyethyl groups, and the like, and R₄₀, R₄₂, and R₄₃ eachare a hydrogen atom or methyl.

Especially preferred of these are the following because the followingoxazoliums are apt to bring about a low coefficient of viscosity:1-ethyloxazolium, 1-propyloxazolium, 1-butyloxazolium,1-pentyloxazolium, 1-hexyloxazolium, 1-allyloxazolium,1-butenyloxazolium, 1-methoxymethyloxazolium, 1-methoxyethyloxazolium,1-ethyl-2,4,5-trimethyloxazolium, 1-propyl-2,4,5-trimethyloxazolium,1-butyl-2,4,5-trimethyloxazolium, 1-pentyl-2,4,5-trimethyloxazolium,1-hexyl-2,4,5-trimethyloxazolium, 1-allyl-2,4,5-trimethyloxazolium,1-butenyl-2,4,5-trimethyloxazolium,1-methoxymethyl-2,4,5-trimethyloxazolium,1-methoxyethyl-2,4,5-trimethyloxazolium, and the like.

Of the thiazolium cations represented by general formula (18), thefollowing are preferred because the following cations are generally aptto form an ambient-temperature-molten salt. Preferred thiazolium cationsare ones in which R₄₅ is any of ethyl, propyl, butyl, pentyl, and hexylgroups, compounds formed by replacing one or more of the hydrogen atomsof each of these alkyl groups with fluorine atoms, vinyl, allyl,butenyl, methoxymethyl, methoxyethyl, ethoxyethyl, methoxyethoxyethyl,and ethoxyethoxyethyl groups, and the like, and R₄₄, R₄₆, and R₄₇ eachare a hydrogen atom or methyl.

Especially preferred of these are the following because the followingthiazoliums are apt to bring about a low coefficient of viscosity:1-ethylthiazolium, 1-propylthiazolium, 1-butylthiazolium,1-pentylthiazolium, 1-hexylthiazolium, 1-allylthiazolium,1-butenylthiazolium, 1-methoxymethylthiazolium,1-methoxyethylthiazolium, 1-ethyl-2,4,5-trimethylthiazolium,1-propyl-2,4,5-trimethylthiazolium, 1-butyl-2,4,5-trimethylthiazolium,1-pentyl-2,4,5-trimethylthiazolium, 1-hexyl-2,4,5-trimethylthiazolium,1-allyl-2,4,5-trimethylthiazolium, 1-butenyl-2,4,5-trimethylthiazolium,1-methoxymethyl-2,4,5-trimethylthiazolium,1-methoxyethyl-2,4,5-trimethylthiazolium, and the like.

Of the pyrazolium cations represented by general formula (19), thefollowing are preferred because the following cations are generally aptto form an ambient-temperature-molten salt. Preferred pyrazolium cationsare ones in which R₄₉ is any of ethyl, propyl, butyl, pentyl, and hexylgroups, compounds formed by replacing one or more of the hydrogen atomsof each of these alkyl groups with fluorine atoms, vinyl, allyl,butenyl, methoxymethyl, methoxyethyl, ethoxyethyl, methoxyethoxyethyl,and ethoxyethoxyethyl groups, and the like, and R₄₈ and R₅₀ to R₅₂ eachare a hydrogen atom or methyl.

Especially preferred of these are the following because the followingpyrazoliums are apt to bring about a low coefficient of viscosity:1-ethylpyrazolium, 1-propylpyrazolium, 1-butylpyrazolium,1-pentylpyrazolium, 1-hexylpyrazolium, 1-allylpyrazolium,1-butenylpyrazolium, 1-methoxymethylpyrazolium,1-methoxyethylpyrazolium, 1-ethyl-2,3,4,5-tetramethylpyrazolium,1-propyl-2,3,4,5-tetramethylpyrazolium,1-butyl-2,3,4,5-tetramethylpyrazolium,1-pentyl-2,3,4,5-tetramethylpyrazolium,1-hexyl-2,3,4,5-tetramethylpyrazolium,1-allyl-2,3,4,5-tetramethylpyrazolium,1-butenyl-2,3,4,5-tetramethylpyrazolium,1-methoxymethyl-2,3,4,5-tetramethylpyrazolium,1-methoxyethyl-2,3,4,5-tetramethylpyrazolium, and the like.

Of the triazolium cations represented by general formula (20), thefollowing are preferred because the following cations are generally aptto form an ambient-temperature-molten salt. Preferred triazolium cationsare ones in which R₅₄ is any of ethyl, propyl, butyl, pentyl, and hexylgroups, compounds formed by replacing one or more of the hydrogen atomsof each of these alkyl groups with fluorine atoms, vinyl, allyl,butenyl, methoxymethyl, methoxyethyl, ethoxyethyl, methoxyethoxyethyl,and ethoxyethoxyethyl groups, and the like, and R₅₃, R₅₅, and R₅₆ eachare a hydrogen atom or methyl.

Especially preferred of these are the following because the followingtriazoliums are apt to bring about a low coefficient of viscosity:1-ethyltriazolium, 1-propyltriazolium, 1-butyltriazolium,1-pentyltriazolium, 1-hexyltriazolium, 1-allyltriazolium,1-butenyltriazolium, 1-methoxymethyltriazolium,1-methoxyethyltriazolium, 1-ethyl-2,3,4,5-tetramethyltriazolium,1-propyl-2,3,4,5-tetramethyltriazolium,1-butyl-2,3,4,5-tetramethyltriazolium,1-pentyl-2,3,4,5-tetramethyltriazolium,1-hexyl-2,3,4,5-tetramethyltriazolium,1-allyl-2,3,4,5-tetramethyltriazolium,1-butenyl-2,3,4,5-tetramethyltriazolium,1-methoxymethyl-2,3,4,5-tetramethyltriazolium,1-methoxyethyl-2,3,4,5-tetramethyltriazolium, and the like.

The anion of the quaternary ammonium salts having a structurerepresented by general formula (7) in invention 5 is not particularlylimited. However, preferred examples thereof include the same anions asthe anions of the lithium salts or the anions of the tertiary sulfoniumsalts having a structure represented by general formula (6).

[Compounds Represented by General Formula (8)]

R_(8r), R_(9r), R_(10r), and R_(11r) in the quaternary phosphoniumcation structure represented by general formula (8) in invention 5 areorganic groups which each have 1-12 carbon atoms and which may be thesame or different. Examples of the R_(8r), R_(9r), R_(10r), and R_(11r)include the same organic groups as those enumerated above with regard tothe “R_(1r), R_(2r), and R_(3r)” in general formula (6) in invention 5,i.e., chain alkyl groups, cycloalkyl groups, alkenyl groups, alkynylgroups, halogenated alkyl groups, aryl groups such as phenyl which mayhave one or more alkyl substituents, aralkyl groups, trialkylsilylgroups, carbonyl-containing alkyl groups, alkyl groups containing one ormore ether groups, and sulfonyl-containing alkyl groups. Preferredexamples thereof also are the same as those enumerated above with regardto the “R_(1r), R_(2r), and R_(3r)” in general formula (6).

It is, however, noted that two to the four of the R_(8r), R_(9r),R_(10r), and R_(11r) may have been bonded to each other to form a ringstructure, and that besides the substituents shown above, a substituentmay have been bonded to R_(8r), R_(9r), R_(10r), and R_(11r) through asaturated or unsaturated bond involving a heteroatom such as oxygen,nitrogen, sulfur, or phosphorus.

A quaternary phosphonium cation structure represented by general formula(8) in invention 5 in which two organic groups of the R_(8r), R_(9r),R_(10r), and R_(11r) actually are one organic group and this one organicgroup has been bonded to the “P⁺” atom through a double bond is alsoincluded in general formula (8) in invention 5. Namely, the case wheretwo of the R_(8r), R_(9r), R_(10r), and R_(11r) have been united witheach other to form an alkylidene group is also included in generalformula (8) in invention 5.

Preferred of those examples of R_(8r) to R_(10r) are alkyl groups having1-10 carbon atoms, halogenated alkyl groups, allyl, and alkyl groupscontaining one or more ether groups. This is because these groups serveto reduce the intermolecular interaction of the phosphonium salt and aregenerally apt to impart a low melting point to the salt.

More preferred of such phosphonium structures are the following becausethe following phosphoniums are apt to bring about a low coefficient ofviscosity: triethylbutylphosphonium, triethylpentylphosphonium,triethylhexylphosphonium, triethylheptylphosphonium,triethyloctylphosphonium, diethylpropylbutylphosphonium,diethylpropylpentylphosphonium, diethylpropylhexylphosphonium,diethylpropylheptylphosphonium, diethylpropyloctylphosphonium,diethylbutylpentylphosphonium, diethylbutylhexylphosphonium,diethylbutylheptylphosphonium, diethylbutyloctylphosphonium,diethylpentylhexylphosphonium, diethylpentylheptylphosphonium,diethylpentyloctylphosphonium, diethylhexylheptylphosphonium,diethylhexyloctylphosphonium, diethylheptyloctylphosphonium,diethyldioctylphosphonium, ethyldipropylbutylphosphonium,ethyldipropylpentylphosphonium, ethyldipropylhexylphosphonium,ethyldipropylheptylphosphonium, ethyldipropyloctylphosphonium,ethylpropyldibutylphosphonium, ethylpropylbutylpentylphosphonium,ethylpropylbutylhexylphosphonium, ethylpropylbutylheptylphosphonium,ethylpropylbutylpeoctylphosphonium, ethylpropyldipentylphosphonium,ethylpropylpentylhexylphosphonium, ethylpropylpentylheptylphosphonium,ethylpropylpentyloctylphosphonium, ethylpropyldihexylphosphonium,ethylpropylhexylheptylphosphonium, ethylpropylhexyloctylphosphonium,ethylpropyldiheptylphosphonium, ethylpropylheptyloctylphosphonium,ethylpropyldioctylphosphonium, ethyltributylphosphonium,ethyldibutylpentylphosphonium, ethyldibutylhexylphosphonium,ethyldibutylheptylphosphonium, ethyldibutyloctylphosphonium,ethylbutyldipentylphosphonium, ethylbutylpentylhexylphosphonium,ethylbutylpentylheptylphosphonium, ethylbutylpentyloctylphosphonium,ethylbutyldihexylphosphonium, ethylbutylhexylheptylphosphonium,ethylbutylhexyloctylphosphonium, ethylbutylheptyloctylphosphonium,ethylbutyldioctylphosphonium, ethyltripentylphosphonium,ethyldipentylhexylphosphonium, ethyldipentylheptylphosphonium,ethyldipentyloctylphosphonium, ethylpentyldihexylphosphonium,ethylpentylhexylheptylphosphonium, ethylpentylhexyloctylphosphonium,ethylpentyldiheptylphosphonium, ethylpentylheptyloctylphosphonium,ethylpentyldioctylphosphonium, ethyltrihexylphosphonium,ethyldihexylheptylphosphonium, ethyldihexyloctylphosphonium,ethylhexyldiheptylphosphonium, ethylhexylheptyloctylphosphonium,ethylhexyldioctylphosphonium, ethyltriheptylphosphonium,ethyldiheptyloctylphosphonium, ethylheptyldioctylphosphonium,ethyltrioctylphosphonium, tripropylbutylphosphonium,tripropylpentylphosphonium, tripropylhexylphosphonium,tripropylheptylphosphonium, tripropyloctylphosphonium,dipropyldibutylphosphonium, dipropylbutylpentylphosphonium,dipropylbutylhexylphosphonium, dipropylbutylheptylphosphonium,dipropylbutyloctylphosphonium, dipropyldipentylphosphonium,dipropylpentylhexylphosphonium, dipropylpentylheptylphosphonium,dipropylpentyloctylphosphonium, dipropyldihexylphosphonium,dipropylhexylheptylphosphonium, dipropylhexyloctylphosphonium,dipropyldiheptylphosphonium, dipropylheptyloctylphosphonium,dipropyldioctylphosphonium, propyltributylphosphonium,propyldibutylpentylphosphonium, propyldibutylhexylphosphonium,propyldibutylheptylphosphonium, propyldibutyloctylphosphonium,propylbutyldipentylphosphonium, propylbutylpentylhexylphosphonium,propylbutylpentylheptylphosphonium, propylbutylpentyloctylphosphonium,propylbutyldiheptylphosphonium, propylbutylheptyloctylphosphonium,propylbutyldioctylphosphonium, propyltripentylphosphonium,propyldipentylhexylphosphonium, propyldipentylheptylphosphonium,propyldipentylheoctylphosphonium, propylpentylhexylheptylphosphonium,propylpentylhexyloctylphosphonium, propylpentyldiheptylphosphonium,propylpentylheptyloctylphosphonium, propylpentyldioctylphosphonium,propyltrihexylphosphonium, propyldihexylheptylphosphonium,propyldihexyloctylphosphonium, propylhexyldiheptylphosphonium,propylhexylheptyloctylphosphonium, propylhexyldioctylphosphonium,propyltriheptylphosphonium, propyldiheptyloctylphosphonium,propylheptyldioctylphosphonium, propyltrioctylphosphonium,tetrabutylphosphonium, tributylpentylphosphonium,tributylhexylphosphonium, tributylheptylphosphonium,tributyloctylphosphonium, tetrapentylphosphonium,tripentylhexylphosphonium, tripentylheptylphosphonium,tripentyloctylphosphonium, tetrahexylphosphonium,trihexylheptylphosphonium, trihexyloctylphosphonium,tetraheptylphosphonium, triheptyloctylphosphonium,tetraoctylphosphonium, compounds formed by replacing one or more of thehydrogen atoms of the alkyl groups of any of these phosphoniums withfluorine atoms, triethylallylphosphonium, triethylbutenylphosphonium,tripropylallylphosphonium, tripropylbutenylphosphonium,tributylallylphosphonium, tributylbutenylphosphonium,triethylmethoxyethylphosphonium, triethylmethoxyethoxyethylphosphonium,tripropylmethoxyethylphosphonium,tripropylmethoxyethoxyethylphosphonium, tributylmethoxyethylphosphonium,tributylmethoxyethoxyethylphosphonium, and the like.

Especially preferred of these are triethylbutylphosphonium,triethylpentylphosphonium, triethylhexylphosphonium,triethylheptylphosphonium, triethyloctylphosphonium,tripropylbutylphosphonium, tripropylpentylphosphonium,tripropylhexylphosphonium, tripropylheptylphosphonium,tripropyloctylphosphonium, tetrabutylphosphonium,tributylpentylphosphonium, tributylhexylphosphonium,tributylheptylphosphonium, tributyloctylphosphonium,tetrapentylphosphonium, tripentylhexylphosphonium,tripentylheptylphosphonium, tripentyloctylphosphonium,tetrahexylphosphonium, trihexylheptylphosphonium,trihexyloctylphosphonium, tetraheptylphosphonium,triheptyloctylphosphonium, tetraoctylphosphonium, compounds formed byreplacing one or more of the hydrogen atoms of the alkyl groups of anyof these phosphoniums with fluorine atoms, triethylallylphosphonium,triethylbutenylphosphonium, tripropylallylphosphonium,tripropylbutenylphosphonium, tributylallylphosphonium,tributylbutenylphosphonium, triethylmethoxyethylphosphonium,triethylmethoxyethoxyethylphosphonium, tripropylmethoxyethylphosphonium,tripropylmethoxyethoxyethylphosphonium, tributylmethoxyethylphosphonium,tributylmethoxyethoxyethylphosphonium, and the like. This is becausethese cations enable the ambient-temperature-molten salt to have amoderate number of ions per unit volume (i.e., ion density) so as not toimpair the features of the ambient-temperature-molten salt. Namely,these cations enable the ambient-temperature-molten salt to have anexcellent balance between melting point and the coefficient ofviscosity.

The anion of the quaternary phosphonium salts having a structurerepresented by general formula (3) in invention 5 is not particularlylimited. However, preferred examples thereof include the same anions asthe anions of the lithium salts, the anions of the tertiary sulfoniumsalts having a structure represented by general formula (1), or theanions of the quaternary ammonium salts having a structure representedby general formula (2).

The nonaqueous solvent in the nonaqueous electrolyte in invention 5 maycontain compounds conventionally known as solvents for nonaqueouselectrolytes, so long as this does not lessen the effects of invention5. In this case, one or more solvents may be suitably selected fromknown solvents for nonaqueous electrolytes and used. Preferred examplesof the nonaqueous solvent include combinations respectively consistingmainly of: an ambient-temperature-molten salt and a chain carbonate; anambient-temperature-molten salt and a cyclic carbonate; anambient-temperature-molten salt and a cyclic ester; anambient-temperature-molten salt and a cyclic sulfone; anambient-temperature-molten salt and a fluorinated chain ether; anambient-temperature-molten salt and a fluorinated chain carbonate; anambient-temperature-molten salt and a polysiloxane having a molecularweight of about 500-3,000; an ambient-temperature-molten salt and apolyether having a molecular weight of about 700-3,000; and anambient-temperature-molten salt and a phosphoric acid ester.

It is preferred that the ambient-temperature-molten salt should becontained in an amount of from 0.01% by mass to 100% by mass based onthe component(s) of the nonaqueous electrolyte excluding both thelithium salt and the “monofluorophosphate and difluorophosphate” whichwill be described later. Examples of the component(s) of the nonaqueouselectrolyte excluding both the lithium salt and the “monofluorophosphateand difluorophosphate” include chain or cyclic carbonates, chain orcyclic esters, chain or cyclic sulfones, chain or cyclic ethers,products of the fluorination of these compounds, “high-boiling solventsand noncombustible solvents” such as polysiloxanes, and polyethers.Examples thereof further include the nonaqueous solvent which will bedescribed later.

The content of the ambient-temperature-molten salt is more preferablyfrom 50% by mass to 100% by mass, especially preferably from 60% by massto 95% by mass, even more preferably from 70% by mass to 90% by mass,based on all the component(s). When the content of theambient-temperature-molten salt is too low, there are cases where theeffect of imparting safety, such as nonflammability and high thermalstability, to the nonaqueous electrolyte is not obtained. On the otherhand, when the content thereof is too high, this nonaqueous electrolytehas too high viscosity, depending on the structure of theambient-temperature-molten salt, and there are cases where thisnonaqueous electrolyte has a reduced ionic conductivity or is less aptto infiltrate into the separator and the positive electrode/negativeelectrode.

In invention 5, one preferred nonaqueous-solvent combination includingan ambient-temperature-molten salt is a combination consisting mainly ofan ambient-temperature-molten salt and a cyclic carbonate. Inparticular, this combination is one in which the proportion of theambient-temperature-molten salt in the nonaqueous solvent is 50% by massor higher, preferably 60% by mass or higher, more preferably 70% by massor higher, and is generally 95% by mass or lower, preferably 90% by massor lower, more preferably 85% by mass or lower. Use of thisnonaqueous-solvent combination is preferred for the following reasons.The nonaqueous electrolyte has a lower coefficient of viscosity than inthe case of using the ambient-temperature-molten salt as the onlysolvent for a nonaqueous electrolyte, and the cyclic carbonate has theeffect of forming a satisfactory coating film on the surface of thenegative electrode. Because of this, the battery produced using thisnonaqueous-solvent combination is satisfactory in high-current densitycharge/discharge capacity and cycle performances.

Examples of the preferred combination of an ambient-temperature-moltensalt and a “cyclic carbonate, cyclic ester, or cyclic sulfone” include:an ambient-temperature-molten salt and ethylene carbonate; anambient-temperature-molten salt and propylene carbonate; anambient-temperature-molten salt and fluoroethylene carbonate; anambient-temperature-molten salt and butylene carbonate; anambient-temperature-molten salt and γ-butyrolactone; anambient-temperature-molten salt and γ-valerolactone; anambient-temperature-molten salt and sulfolane; and anambient-temperature-molten salt and fluorosulfolane.

Another preferred combination is a combination consisting mainly of anambient-temperature-molten salt and a fluorinated chain ether. Inparticular, this combination is one in which the proportion of theambient-temperature-molten salt in the nonaqueous solvent is 50% by massor higher, preferably 60% by mass or higher, more preferably 70% by massor higher, and is generally 95% by mass or lower, preferably 90% by massor lower, more preferably 85% by mass or lower. Use of thisnonaqueous-solvent combination is preferred for the following reasons.This nonaqueous-solvent combination enables the nonaqueous electrolyteto have a lower coefficient of viscosity than in the case of using theambient-temperature-molten salt as the only solvent for a nonaqueouselectrolyte, without impairing the nonflammability of theambient-temperature-molten salt, and this nonaqueous electrolyte is moreapt to infiltrate into pores of the positive electrode and negativeelectrode. Because of this, the battery produced using thisnonaqueous-solvent combination has improved high-current densitycharge/discharge capacity.

Examples of the preferred combination of an ambient-temperature-moltensalt and a fluorinated chain ether include: anambient-temperature-molten salt and nonafluorobutyl methyl ether; anambient-temperature-molten salt and nonafluorobutyl ethyl ether; anambient-temperature-molten salt and trifluoroethoxyethoxymethane; anambient-temperature-molten salt and trifluoroethoxyethoxyethane; anambient-temperature-molten salt and hexafluoroethoxyethoxymethane; andan ambient-temperature-molten salt and hexafluoroethoxyethoxyethane.

Examples of the preferred combination of an ambient-temperature-moltensalt and a phosphoric acid ester include: an ambient-temperature-moltensalt and trimethyl phosphate; an ambient-temperature-molten salt andtriethyl phosphate; an ambient-temperature-molten salt and dimethylethyl phosphate; an ambient-temperature-molten salt and methyl diethylphosphate; an ambient-temperature-molten salt and tristrifluoroethylphosphate; an ambient-temperature-molten salt and ethylene methylphosphate; an ambient-temperature-molten salt and ethylene ethylphosphate; an ambient-temperature-molten salt and trihexyl phosphate;and an ambient-temperature-molten salt and trioctyl phosphate.

<1-3. Monofluorophosphate and Difluorophosphate>

The nonaqueous electrolyte in invention 5 contains a“monofluorophosphate and/or difluorophosphate” besides the lithium saltand ambient-temperature-molten salt described above.

The counter cations of the monofluorophosphate and difluorophosphate arenot particularly limited. Examples thereof include metal elements suchas Li, Na, K, Mg, Ca, Fe, and Cu, and further include tertiarysulfoniums represented by general formula (6), quaternary ammoniumsrepresented by general formula (7), and quaternary phosphoniumsrepresented by general formula (8). The counter cations represented bygeneral formulae (6) to (8) are the same as the structures usable in theambient-temperature-molten salt.

Preferred of those counter cations, from the standpoint of thecharacteristics of the battery employing the nonaqueous electrolyte, arelithium, sodium, potassium, magnesium, calcium, or the tertiarysulfoniums, quaternary ammoniums, or quaternary phosphoniums. Lithium isespecially preferred.

Of such monofluorophosphates and difluorophosphates, thedifluorophosphates are preferred from the standpoints of the cycleperformances, high-temperature storability, etc. of the battery.Especially preferred is lithium difluorophosphoate. Such compoundssynthesized in a nonaqueous solvent may be used substantially as theyare. Alternatively, such a compound which has been separatelysynthesized and substantially isolated may be added to a nonaqueoussolvent or to a nonaqueous electrolyte.

The amount of the “monofluorophosphate and/or difluorophosphate” to beincorporated, based on the whole nonaqueous electrolyte of invention 5,is not limited, and may be any desired value unless this considerablylessens the effects of invention 5. However, the monofluorophosphateand/or difluorophosphate is incorporated in a total concentration whichis generally 0.001% by mass or higher, preferably 0.01% by mass orhigher, more preferably 0.1% by mass or higher, and is generally 20% bymass or lower, preferably 10% by mass or lower, more preferably 5% bymass or lower, based on the whole nonaqueous electrolyte of invention 5.When the amount thereof is too large, there are cases where the saltsprecipitate at low temperatures to reduce battery characteristics. Onthe other hand, when the amount thereof is too small, there are caseswhere the effect of improving cycle performances, high-temperaturestorability, etc. decreases considerably. It is, however, noted thatwhen the monofluorophosphate and/or difluorophosphate serves also as anambient-temperature-molten salt, this ingredient is incorporated in aconcentration which is generally 0.001% by mass or higher, preferably0.01% by mass or higher, more preferably 0.1% by mass or higher, and isgenerally 100% by mass or lower, preferably 95% by mass or lower, morepreferably 90% by mass or lower, especially preferably 85% by mass orlower. When the amount thereof is too large, there are cases where thisnonaqueous electrolyte has increased viscosity to have a reduced ionicconductivity or be less apt to infiltrate into the separator and thepositive electrode/negative electrode. On the other hand, when theamount thereof is too small, there are cases where the effect ofimproving low-temperature characteristics, cycle performances,high-temperature storability, etc. decreases considerably as in the casedescribed above.

The molecular weight of the monofluorophosphate or difluorophosphate,processes for producing the salt, etc. are the same as those describedabove with regard to invention 1.

Furthermore, the time at which a monofluorophosphate ordifluorophosphate is detected (the time at which the salt is contained),the place into which the salt is incorporated first (derivation ofcontainment), means of incorporating the salt, detection places based onwhich the salt is considered to be contained (or have been contained) inthe nonaqueous electrolyte, etc. are also the same as those describedabove with regard to invention 1.

<1-4. Other Compounds>

The nonaqueous electrolyte of invention 5 can contain “other compounds”so long as this does not lessen the effects of invention 5. Examples ofsuch “other compounds” include conventionally known various compoundssuch as negative-electrode coating agents, positive-electrode protectiveagents, overcharge inhibitors, and aids.

<1-4-1. Negative-Electrode Coating Agent>

By incorporating a negative-electrode coating agent, the reversibilityof lithium ion reactions occurring at the negative electrode can beimproved and charge/discharge capacity, charge/discharge efficiency, andcycle performances can be improved. Preferred examples of thenegative-electrode coating agent include vinylene carbonate,vinylethylene carbonate, and fluoroethylene carbonate. One of suchnegative-electrode coating agents may be used alone, or any desiredcombination of two or more thereof in any desired proportion may beused.

The content of these negative-electrode coating agents in the nonaqueouselectrolyte is not particularly limited. However, the content of eachnegative-electrode coating agent maybe 0.01% by mass or higher,preferably 0.1% by mass or higher, more preferably 0.2% by mass orhigher, based on the whole nonaqueous electrolyte. The upper limitthereof may be 12% by mass or lower, preferably 10% by mass or lower,more preferably 8% by mass or lower.

<1-4-2. Positive-Electrode Protective Agent>

By incorporating a positive-electrode protective agent, capacityretention and cycle performances after high-temperature storage can beimproved. Preferred examples of the positive-electrode protective agentinclude ethylene sulfite, propylene sulfite, propanesultone,butanesultone, methyl methanesulfonate, and busulfan. Two or more ofthese may be used in combination.

The content of these positive-electrode protective agents in thenonaqueous electrolyte is not particularly limited. However, the contentof each positive-electrode protective agent may be 0.01% by mass orhigher, preferably 0.1% by mass or higher, more preferably 0.2% by massor higher, based on the whole nonaqueous electrolyte. The upper limitthereof may be 5% by mass or lower, preferably 3% by mass or lower, morepreferably 2% by mass or lower.

<1-4-3. Overcharge Inhibitor>

By incorporating an overcharge inhibitor, the battery can be inhibitedfrom rupturing/igniting upon overcharge, etc.

Examples of the overcharge inhibitor include those enumerated above withregard to invention 1. The proportion of the overcharge inhibitor in thenonaqueous electrolyte is generally 0.1% by mass or higher, preferably0.2% by mass or higher, especially preferably 0.3% by mass or higher,most preferably 0.5% by mass or higher, based on the whole nonaqueouselectrolyte. The upper limit thereof is generally 5% by mass or lower,preferably 3% by mass or lower, especially preferably 2% by mass orlower. In case where the concentration thereof is lower than the lowerlimit, the overcharge inhibitor produces almost no effect. Conversely,in case where the concentration thereof is too high, batterycharacteristics such as high-temperature storability tend to decrease.

<1-4-4. Aids>

Examples of the aids include those enumerated above with regard toinvention 1. Two or more of these may be used in combination. Of theseaids, it is preferred to add a carbonate having at least one of anunsaturated bond and a halogen atom (hereinafter sometimes referred toas “specific carbonate”) as an aid for improving capacity retentionafter high-temperature storage and cycle performances. Examples of thespecific carbonate are the same as in invention 1.

The proportion of these aids in the nonaqueous electrolyte is generally0.01% by mass or higher, preferably 0.1% by mass or higher, especiallypreferably 0.2% by mass or higher, based on the whole nonaqueouselectrolyte. The upper limit thereof is generally 5% by mass or lower,preferably 3% by mass or lower, especially preferably 1% by mass orlower. By adding those aids, capacity retention after high-temperaturestorage and cycle performances can be improved. In case where theconcentration thereof is lower than the lower limit, the aids producealmost no effect. Conversely, in case where the concentration thereof istoo high, battery characteristics such as high-load dischargecharacteristics tend to decrease.

<1-5. Preparation of Nonaqueous Electrolyte>

The nonaqueous electrolyte in invention 5 can be prepared by dissolvinga lithium salt, an ambient-temperature-molten salt, amonofluorophosphate or difluorophosphate in each other optionallytogether with “other compounds”. It is preferred that in preparing thenonaqueous electrolyte, each of the raw materials should be dehydratedbeforehand in order to reduce the water content of the nonaqueouselectrolyte to be obtained. It is desirable to dehydrate each rawmaterial to generally 50 ppm or lower, preferably 30 ppm or lower,especially preferably 10 ppm or lower. It is also possible to conductdehydration, deacidification, and the like after the preparation of anonaqueous electrolyte.

The nonaqueous electrolyte of invention 5 is suitable for use as anelectrolyte for nonaqueous-electrolyte batteries, in particular, forsecondary batteries, e.g., lithium secondary batteries. Thenonaqueous-electrolyte battery employing the nonaqueous electrolyte ofinvention 5 is explained below.

<1-6. Process for Producing Nonaqueous Electrolyte>

For producing the nonaqueous electrolyte of invention 5, the sameprocess as in invention 1 can be used.

[2. Nonaqueous-Electrolyte Secondary Battery]

The nonaqueous-electrolyte secondary battery of invention 5 includes: anegative electrode and a positive electrode which are capable ofoccluding and releasing ions; and the nonaqueous electrolyte ofinvention 5 described above.

The following are the same as those described above with regard toinvention 1: battery constitution; negative electrode; carbonaceousmaterial; constitution and properties of carbonaceous negative electrodeand method of preparation thereof; metal compound material, constitutionand properties of negative electrode employing metal compound material,and method of preparation thereof; positive electrode; separator;battery design; and the like.

[Current Collector Structure]

The current collector structure is not particularly limited. However,for more effectively realizing the improvement in high-current-densitycharge/discharge characteristics which is brought about by thenonaqueous electrolyte of invention 5, it is preferred to employ astructure reduced in the resistance of wiring parts and joint parts. Inthe case where internal resistance has been reduced in this manner, useof the nonaqueous electrolyte of invention 5 produces its effectsespecially satisfactorily.

In the case of electrode groups assembled into the multilayer structuredescribed above, a structure obtained by bundling the metallic coreparts of respective electrode layers and welding the bundled parts to aterminal is suitable. When each electrode has a large area, this resultsin increased internal resistance. In this case, it is preferred todispose two or more terminals in each electrode to reduce theresistance. In the case of an electrode group having the wound structuredescribed above, two or more lead structures may be disposed on each ofthe positive electrode and negative electrode and bundled into aterminal, whereby internal resistance can be reduced.

By optimizing the structure described above, internal resistance can beminimized. In batteries to be used at a heavy current, it is preferredthat the impedance thereof as measured by the 10-kHz alternating-currentmethod (hereinafter referred to as “direct-current resistancecomponent”) should be regulated to 10 milliohms (mΩ) or lower. It ismore preferred to regulate the direct-current resistance componentthereof to 5 mΩ or lower. When the direct-current resistance componentis reduced to 0.1 mΩ or lower, output characteristics improve. However,this regulation results in an increased proportion of current collectorstructure materials and may reduce the battery capacity.

[Function]

According to invention 5, a “monofluorophosphate and/ordifluorophosphate”, which each has, for example, the effect of reducinginterfacial resistance and the effect of improving suitability forcharge/discharge cycling, is incorporated into a nonaqueous electrolytecomprising an ambient-temperature-molten salt. Although the mechanism bywhich invention 5 produces these effects is not clear and althoughinvention 5 should not be construed as being limited by the followingmechanism, the following is thought. The monofluorophosphate ordifluorophosphate, among the compounds constituting the nonaqueouselectrolyte, preferentially acts on the electrodes and is concentratedat the electrode interfaces or adsorbed onto the electrode surfaces. Thesalt thereby prevents the positive-electrode active material fromdissolving away in the nonaqueous electrolyte and inhibits electronconduction paths from breaking due to volume changes of the electrodeactive material with charge/discharge. In the case of lithiummonofluorophosphate or lithium difluorophosphate, this salt has thefunction of heightening lithium concentration on an electrode surface.These are presumed to give the effects of reducing interfacialresistance and improving suitability for charge/discharge cycling. Inaddition, since the monofluorophosphate and difluorophosphate areinorganic substances, this electrolyte is free from the evolution of anycombustible gas derived from the decomposition of these salts.

Lithium monofluorophosphate and lithium difluorophosphate haveexceedingly low solubility in general nonaqueous electrolytes includinga cyclic carbonate such as ethylene carbonate and a chain carbonate suchas dimethyl carbonate as main components. However, the lithium salts canbe dissolved in a larger amount in ambient-temperature-molten salts thanin the organic-solvent electrolytes. In addition, a monofluorophosphateanion or difluorophosphate anion may be used as the counter anion of anambient-temperature-molten salt. By thus using a monofluorophosphate ordifluorophosphate and an ambient-temperature-molten salt in combination,the effects of reducing interfacial resistance and improvingcharge/discharge cycle performances can be brought about more remarkablyand synergistically.

Examples

The invention will be explained below in more detail by reference toExamples and Comparative Examples. However, the invention should not beconstrued as being limited to the following Examples unless theinvention departs from the spirit thereof.

[With Respect to Invention 1] [Production of Positive Electrode]

Ninety-two parts by weight of lithium cobalt oxide (LiCoO₂) was mixedwith 4 parts by weight of poly(vinylidene fluoride) (hereinafterabbreviated to “PVdF”) and 4 parts by weight of acetylene black.N-Methylpyrrolidone was added to the mixture to slurry it. This slurrywas applied to each side of a current collector made of aluminum, andthe coating was dried to obtain a positive electrode.

[Production of Negative Electrode]

Ninety-two parts by weight of a graphite powder was mixed with 8 partsby weight of PVdF, and N-methylpyrrolidone was added to the mixture toslurry it. This slurry was applied to one side of a current collectormade of copper, and the coating was dried to obtain a negativeelectrode.

[Production of Nonaqueous-Electrolyte Secondary Battery]

The positive electrode and negative electrode described above and aseparator made of polyethylene were superposed in the order of negativeelectrode/separator/positive electrode/separator/negative electrode. Thebattery element thus obtained was wrapped in a cylindricalaluminum-laminated film. The electrolyte which will be described laterwas introduced into this package, which was then vacuum-sealed. Thus, asheet-form nonaqueous-electrolyte secondary battery was produced.Furthermore, this sheet battery was pressed by being sandwiched betweenglass plates, in order to enhance contact between the electrodes.

[Capacity Evaluation]

In a 25° C. thermostatic chamber, the sheet-form nonaqueous-electrolytesecondary battery was subjected to constant-current constant-voltagecharge (hereinafter suitably referred to as “CCCV charge”) to 4.4 V at0.2 C and then discharged to 3.0 V at 0.2 C. This operation was repeatedthree times to conduct conditioning. Subsequently, this battery wassubjected again to CCCV charge to 4.4 V at 0.7 C and discharged again to3.0 V at 1 C to determine initial discharge capacity. The cutoff currentin each charging operation was set at 0.05 C. Incidentally, “1 C” meansa current value at which the whole capacity of the battery is dischargedover 1 hour.

[Evaluation of Cycle Performances]

The battery which had undergone the capacity evaluation test was placedin a 25° C. thermostatic chamber and repeatedly subjected to 50 cyclesof charge/discharge in each of which the battery was charged by CCCVcharge to 4.4 V at 0.7 C and discharged to 3 V at a constant current of1 C. The capacity retention after the 50 cycles was determined accordingto the following calculation equation. Based on this value, cycleperformances were evaluated. The larger the value of this property, thelower the cycle deterioration of the battery.

Capacity retention after 50 cycles (%)=[(discharge capacity in 50thcycle (mAh/g))/(discharge capacity in 1st cycle (mAh/g))]×100

Example 1 of Invention 1

LiPF₆ as an electrolyte was dissolved, in a proportion of 1 mol/L, in amixed solvent composed of ethylene carbonate (EC) and ethyl methylcarbonate (EMC) (mixing volume ratio, 2:8). This solution is referred toas base electrolyte (I). A nonaqueous electrolyte was prepared by addinglithium difluorophosphate (LiPO₂F₂) and nickel (II) hexafluorophosphate(Ni(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 20 ppm (corresponding to Nielement concentration of 3.4 ppm), respectively, based on the nonaqueouselectrolyte. Using the nonaqueous electrolyte obtained, anonaqueous-electrolyte secondary battery was produced by the methoddescribed above. This battery was subjected to the capacity evaluationand the evaluation of cycle performances. The results thereof are shownin Table 1.

Example 2 of Invention 1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and nickel (II) hexafluorophosphate(Ni(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 50 ppm (corresponding to Nielement concentration of 8.4 ppm), respectively, based on the nonaqueouselectrolyte. Using this nonaqueous electrolyte, a nonaqueous-electrolytesecondary battery was produced by the method described above. Thisbattery was subjected to the capacity evaluation and the evaluation ofcycle performances. The results thereof are shown in Table 1.

Example 3 of Invention 1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and nickel (II) hexafluorophosphate(Ni(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 100 ppm (corresponding to Nielement concentration of 16.8 ppm), respectively, based on thenonaqueous electrolyte. Using this nonaqueous electrolyte, anonaqueous-electrolyte secondary battery was produced by the methoddescribed above. This battery was subjected to the capacity evaluationand the evaluation of cycle performances. The results thereof are shownin Table 1.

Example 4 of Invention 1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and nickel (II) hexafluorophosphate(Ni(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 200 ppm (corresponding to Nielement concentration of 33.7 ppm), respectively, based on thenonaqueous electrolyte. Using this nonaqueous electrolyte, anonaqueous-electrolyte secondary battery was produced by the methoddescribed above. This battery was subjected to the capacity evaluationand the evaluation of cycle performances. The results thereof are shownin Table 1.

Example 5 of Invention 1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and nickel (II) hexafluorophosphate(Ni(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 300 ppm (corresponding to Nielement concentration of 50.5 ppm), respectively, based on thenonaqueous electrolyte. Using this nonaqueous electrolyte, anonaqueous-electrolyte secondary battery was produced by the methoddescribed above. This battery was subjected to the capacity evaluationand the evaluation of cycle performances. The results thereof are shownin Table 1.

Example 6 of Invention 1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and nickel (II) hexafluorophosphate(Ni(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 1,000 ppm (corresponding to Nielement concentration of 168 ppm), respectively, based on the nonaqueouselectrolyte. Using this nonaqueous electrolyte, a nonaqueous-electrolytesecondary battery was produced by the method described above. Thisbattery was subjected to the capacity evaluation and the evaluation ofcycle performances. The results thereof are shown in Table 1.

Example 7 of Invention 1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and nickel (II) hexafluorophosphate(Ni(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 3,500 ppm (corresponding to Nielement concentration of 589 ppm), respectively, based on the nonaqueouselectrolyte. Using this nonaqueous electrolyte, a nonaqueous-electrolytesecondary battery was produced by the method described above. Thisbattery was subjected to the capacity evaluation and the evaluation ofcycle performances. The results thereof are shown in Table 1.

Example 8 of Invention 1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and nickel (II) hexafluorophosphate(Ni(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 10,000 ppm (corresponding to Nielement concentration of 1,684 ppm), respectively, based on thenonaqueous electrolyte. Using this nonaqueous electrolyte, anonaqueous-electrolyte secondary battery was produced by the methoddescribed above. This battery was subjected to the capacity evaluationand the evaluation of cycle performances. The results thereof are shownin Table 1.

Example 9 of Invention 1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and cobalt (II) hexafluorophosphate(Co(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 50 ppm (corresponding to Coelement concentration of 8.4 ppm), respectively, based on the nonaqueouselectrolyte. Using this nonaqueous electrolyte, a nonaqueous-electrolytesecondary battery was produced by the method described above. Thisbattery was subjected to the capacity evaluation and the evaluation ofcycle performances. The results thereof are shown in Table 1.

Example 10 of Invention 1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and cobalt (II) hexafluorophosphate(Co(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 100 ppm (corresponding to Coelement concentration of 16.9 ppm), respectively, based on thenonaqueous electrolyte. Using this nonaqueous electrolyte, anonaqueous-electrolyte secondary battery was produced by the methoddescribed above. This battery was subjected to the capacity evaluationand the evaluation of cycle performances. The results thereof are shownin Table 1.

Comparative Example 1 for Invention 1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) only to the base electrolyte (I) in aconcentration of 0.5% by mass based on the nonaqueous electrolyte. Usingthis nonaqueous electrolyte, a nonaqueous-electrolyte secondary batterywas produced by the method described above. This battery was subjectedto the capacity evaluation and the evaluation of cycle performances. Theresults thereof are shown in Table 1.

Comparative Example 2 for Invention 1

A nonaqueous electrolyte was prepared by adding nickel (II)hexafluorophosphate (Ni(PF₆)₂) only as an iron-group element compound tothe base electrolyte (I) in a concentration of 100 ppm (corresponding toNi element concentration of 16.8 ppm) based on the nonaqueouselectrolyte. Using this nonaqueous electrolyte, a nonaqueous-electrolytesecondary battery was produced by the method described above. Thisbattery was subjected to the capacity evaluation and the evaluation ofcycle performances. The results thereof are shown in Table 1.

TABLE 1 Iron-group element Capacity Concentration of retentionMonofluorophosphate iron-group element Concentration of after ordifluorophosphate Kind of iron-group compound iron-group element cyclingNo. (mass %) element compound (ppm) (ppm) (%) Example 1 LiPO₂F₂ 0.5%Ni(PF₆)₂ 20 3.4 95.1 Example 2 LiPO₂F₂ 0.5% Ni(PF₆)₂ 50 8.4 95.8 Example3 LiPO₂F₂ 0.5% Ni(PF₆)₂ 100 16.8 96.3 Example 4 LiPO₂F₂ 0.5% Ni(PF₆)₂200 33.7 95.2 Example 5 LiPO₂F₂ 0.5% Ni(PF₆)₂ 300 50.5 94.6 Example 6LiPO₂F₂ 0.5% Ni(PF₆)₂ 1000 168 94.0 Example 7 LiPO₂F₂ 0.5% Ni(PF₆)₂ 3500589 93.7 Example 8 LiPO₂F₂ 0.5% Ni(PF₆)₂ 10000 1684 93.0 Example 9LiPO₂F₂ 0.5% Co(PF₆)₂ 50 8.4 95.1 Example 10 LiPO₂F₂ 0.5% Co(PF₆)₂ 10016.9 95.5 Comparative Example 1 LiPO₂F₂ 0.5% none 0 0 92.2 ComparativeExample 2 none Ni(PF₆)₂ 100 16.8 88.6

As apparent from Table 1, the following was found. Thenonaqueous-electrolyte secondary batteries of Example 1 to Example 10 ofinvention 1, which employed nonaqueous electrolytes of invention 1containing an iron-group element and a “monofluorophosphate and/ordifluorophosphate”, had better cycle performances (capacity retentionafter cycling) than the nonaqueous-electrolyte secondary batteriescontaining a difluorophosphate only (Comparative Example 1 forInvention 1) or containing an iron-group element only (ComparativeExample 2 for Invention 1).

[With Respect to Invention 1-1] Example 1 of Invention 1-1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and nickel (II) hexafluorophosphate(Ni(PF₆)₂) as an iron-group element compound to the same baseelectrolyte (I) as in Example 1 of Invention 1 in concentrations of 0.5%by mass and 0.1 ppm (corresponding to Ni element concentration of 0.02ppm), respectively, based on the nonaqueous electrolyte. Using thenonaqueous electrolyte obtained, a nonaqueous-electrolyte secondarybattery was produced by the method described in the Examples ofInvention 1. This battery was subjected to the capacity evaluation andthe evaluation of cycle performances. The results obtained are shown inTable 1-1.

Example 2 of Invention 1-1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and nickel (II) hexafluorophosphate(Ni(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 1 ppm (corresponding to Ni elementconcentration of 0.17 ppm), respectively, based on the nonaqueouselectrolyte. Using this nonaqueous electrolyte, a nonaqueous-electrolytesecondary battery was produced by the method described in the Examplesof Invention 1. This battery was subjected to the capacity evaluationand the evaluation of cycle performances. The results obtained are shownin Table 1-1.

Example 3 of Invention 1-1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and nickel (II) hexafluorophosphate(Ni(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 3 ppm (corresponding to Ni elementconcentration of 0.51 ppm), respectively, based on the nonaqueouselectrolyte. Using this nonaqueous electrolyte, a nonaqueous-electrolytesecondary battery was produced by the method described in the Examplesof Invention 1. This battery was subjected to the capacity evaluationand the evaluation of cycle performances. The results obtained are shownin Table 1-1.

Example 4 of Invention 1-1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and nickel (II) hexafluorophosphate(Ni(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 5 ppm (corresponding to Ni elementconcentration of 0.84 ppm), respectively, based on the nonaqueouselectrolyte. Using this nonaqueous electrolyte, a nonaqueous-electrolytesecondary battery was produced by the method described in the Examplesof Invention 1. This battery was subjected to the capacity evaluationand the evaluation of cycle performances. The results obtained are shownin Table 1-1.

Example 5 of Invention 1-1

A nonaqueous electrolyte was prepared by adding lithiumdifluorophosphate (LiPO₂F₂) and cobalt (II) hexafluorophosphate(Co(PF₆)₂) as an iron-group element compound to the base electrolyte (I)in concentrations of 0.5% by mass and 3 ppm (corresponding to Co elementconcentration of 0.51 ppm), respectively, based on the nonaqueouselectrolyte. Using this nonaqueous electrolyte, a nonaqueous-electrolytesecondary battery was produced by the method described in the Examplesof Invention 1. This battery was subjected to the capacity evaluationand the evaluation of cycle performances. The results obtained are shownin Table 1-1.

TABLE 1-1 Iron-group element in nonaqueous electrolyteMonofluorophosphoric Concentration Concentration Capacity acid salt ofiron- of iron- retention or difluorophosphoric Kind of iron-family-element family after acid salt family-element compound elementcycling No. (mass %) compound (ppm) (ppm) (%) Example 1 LiPO₂F₂: 0.5Ni(PF₆)₂ 0.1 0.02 93.8 Example 2 LiPO₂F₂: 0.5 Ni(PF₆)₂ 1 0.17 94.2Example 3 LiPO₂F₂: 0.5 Ni(PF₆)₂ 3 0.51 95.2 Example 4 LiPO₂F₂: 0.5Ni(PF₆)₂ 5 0.84 94.9 Example 5 LiPO₂F₂: 0.5 Co(PF₆)₂ 3 0.51 94.5Comparative LiPO₂F₂: 0.5 none 0 0 92.2 Example 1 Comparative noneNi(PF₆)₂ 100 16.8 88.6 Example 2

In Table 1-1, Comparative Examples 1 and 2 are Comparative Examples 1and 2 for Invention 1.

As apparent from Table 1-1, it was found that the nonaqueous-electrolytesecondary batteries of Example 1 to Example 5, which employed nonaqueouselectrolytes of invention 1-1 containing a specific amount of an“iron-group element” and a “monofluorophosphate and/ordifluorophosphate”, had better cycle performances (capacity retentionafter cycling) than the nonaqueous-electrolyte secondary batteriesemploying nonaqueous electrolytes containing a difluorophosphate only(Comparative Example 1 for Invention 1) or containing an iron-groupelement only (Comparative Example 2 for Invention 1).

[With Respect to Invention 2] Example 1 of Invention 2 <Production ofNonaqueous-Electrolyte Secondary Battery> [Production ofPositive-Electrode Active Material]

As a positive-electrode active material was used a lithium-transitionmetal composite oxide represented by the composition formulaLiMn_(0.33)Ni_(0.33)Co_(0.33)O₂. This positive-electrode active materialwas synthesized by the following method. Mn₃O₄, NiO, and Co(OH)₂ wereweighed out as a manganese source, nickel source, and cobalt source,respectively, in such amounts as to result in an Mn:Ni:Co molar ratio of1:1:1. Pure water was added thereto to prepare a slurry. Using acirculating medium-stirring type wet bead mill, the solid matters in theslurry were wet-pulverized with stirring to a median diameter of 0.2 μm.

The slurry was spray-dried with a spray dryer to obtain nearly sphericalgranulated particles having a particle diameter of about 5 μm consistingonly of the manganese source, nickel source, and cobalt source. An LiOHpowder having a median diameter of 3 μm was added to the resultantgranulated particles in such an amount that the ratio of the number ofmoles of the Li to the total number of moles of the Mn, Ni, and Cobecame 1.05 times. The ingredients were mixed together by means of ahigh-speed mixer to obtain a powder mixture of the lithium source andthe granulated particles of the nickel source, cobalt source, andmanganese source. This powder mixture was burned at 950° C. for 12 hours(heating/cooling rate, 5° C./min) in an air stream, subsequentlydisaggregated, and passed through a sieve having an opening size of 45μm to obtain a positive-electrode active material.

[Production of Positive Electrode]

Ninety percents by mass the positive-electrode active material was mixedwith 5% by mass acetylene black as a conductive material and 5% by masspoly(vinylidene fluoride) (PVdF) as a binder in N-methylpyrrolidonesolvent to prepare a slurry. The slurry obtained was applied to one sideof an aluminum foil having a thickness of 15 μm and dried. The coatedfoil was rolled with a pressing machine to a thickness of 80 μm. Diskshaving a diameter of 12.5 mm were punched out of the coated foil with apunching die to produce positive electrodes. Part of these positiveelectrodes was used together with a lithium metal sheet as a counterelectrode and a porous polyethylene film having a thickness of 25 μm asa separator to fabricate a coin cell. For this cell was used anelectrolyte prepared by dissolving LiPF₆ in a concentration of 1 mol/Lin a solvent composed of EC (ethylene carbonate)/DMC (dimethylcarbonate)/EMC (ethyl methyl carbonate)=3/3/4 (volume ratio).

The coin cell obtained was subjected to constant-currentconstant-voltage charge at 0.2 mA/cm², i.e., a reaction in which lithiumions were released from the positive electrode, to an upper limit of 4.2V. Subsequently, the cell was subjected to constant-current discharge at0.2 mA/cm², i.e., a reaction in which lithium ions were occluded in thepositive electrode, to a lower limit of 3.0 V. The initial chargecapacity and initial discharge capacity per unit weight of thepositive-electrode active material which were determined in thecharge/discharge are expressed by Qs (C) [mAh/g] and Qs (D) [mAh/g],respectively.

[Production of Negative Electrode]

To 98 parts by weight of artificial-graphite powder KS-44 (trade name;manufactured by Timcal) were added 100 parts by weight of an aqueousdispersion of sodium carboxymethyl cellulose (concentration of sodiumcarboxymethyl cellulose, 1% by mass) as a thickener and 2 parts byweight of an aqueous dispersion of a styrene/butadiene rubber(concentration of styrene/butadiene rubber, 50% by mass) as a binder.The ingredients were mixed together by means of a disperser to obtain aslurry. The slurry obtained was applied to a side of a copper foilhaving a thickness of 10 μm and dried. The coated foil was rolled with apressing machine to a thickness of 75 μm. Disks having a diameter of12.5 mm were punched out of the coated foil with a punching die toproduce negative electrodes.

Part of these negative electrodes was used as a test electrode togetherwith lithium metal as a counter electrode to fabricate a battery cell.This cell was subjected to a test in which lithium ions were occluded inthe negative electrode by the constant-current constant-voltage methodat 0.2 mA/cm² and 3 mV (cutoff current, 0.05 mA) to a lower limit of 0V. The initial occlusion capacity per unit weight of thenegative-electrode active material in this test is expressed by Qf[mAh/g].

[Nonaqueous Electrolyte]

In a dry argon atmosphere, sufficiently dried LiPF₆ was mixed, in aproportion of 1 mol/L, with a mixture of ethylene carbonate, dimethylcarbonate, and ethyl methyl carbonate (volume ratio, 3:3:4). A targetelectrolyte was obtained by incorporating heptane, as a compoundselected from the compounds of invention 2, into the resultant mixturesolution so as to result in a proportion thereof of 2% by mass based onthe whole nonaqueous electrolyte and dissolving lithiumdifluorophosphate in the solution so as to result in a concentrationthereof of 0.2% by mass based on the whole nonaqueous electrolyte.

[Battery Assembly]

A battery to be tested was fabricated using a combination of thepositive electrode and negative electrode produced above and using acoin cell, and was evaluated for battery performances. Namely, thepositive electrode produced was placed on a positive-electrode can for acoin cell, and a porous polyethylene film having a thickness of 25 μmwas placed thereon as a separator. This assemblage was pressed with agasket made of polypropylene. Thereafter, the nonaqueous electrolytedescribed above was introduced into the can and sufficiently infiltratedinto the separator. Subsequently, the negative electrode described abovewas placed and a negative-electrode can was placed thereon and sealed.Thus, a coin type lithium secondary battery was produced. In thisfabrication, the balance between the weight of the positive-electrodeactive material and the weight of the negative-electrode active materialwas set so that the following expression was almost satisfied.

[(Weight of negative-electrode active material [g])×(Qf[mAh/g])]/[(weight of positive-electrode active material [g])×(Qs(C)[mAh/g])]=1.2

<Battery Characteristics Test>

In order to examine the low-temperature load characteristics of thebattery thus obtained, the 1-hour-rate current value, i.e., 1 C, of thebattery was set as shown by the following equation and the followingtest was made.

1 C [mA]=Qs(D)×(weight of positive-electrode active material [g])/h

First, at room temperature, the battery was subjected to one cycle ofconstant-current charge/discharge at 0.2 C and thereafter subjected totwo cycles each consisting of constant-current constant-voltage chargeat C/3 and subsequent constant-current discharge at C/3. The finalcharge voltage and final discharge voltage were set at 4.1 V and 3.0 V,respectively.

(Output Test)

Subsequently, the coil cell which had been regulated so as to have astate of charge of 50% by C/3 constant-current charge was subjected toan output measurement test in a 25° C. environment. The cell wasdischarged for 10 seconds at each of 0.3 C, 1.0 C, 3.0 C, and 10.0 C,and the voltage thereof was measured at 10 seconds after the dischargeinitiation (after each discharge, the cell was paused for 15 minutes,subsequently charged in a quantity of electricity corresponding to thedischarge, and then paused for 15 minutes before being subjected to thenext discharge test). The area of the triangle surrounded by theresultant current-voltage straight line and the final discharge voltage(3 V) was taken as initial output (W). The results thereof are shown inTable 2.

(Cycle Test)

A cycle test was conducted in a high-temperature environment of 60° C.,which is regarded as the upper-limit temperature for the actual use oflithium secondary batteries. The cell was charged by theconstant-current constant-voltage method at 2 C to a final chargevoltage of 4.1 V and then discharged at a constant current of 2 C to afinal discharge voltage of 3.0 V. This charge/discharge operation as onecycle was repeated to conduct 100 cycles in total. The cell which hadundergone the cycle test was subjected to three charge/discharge cyclesin a 25° C. environment at C/3, and the output thereof was measured inthe same manner as for the initial output. This output is referred to asoutput after cycling. The results thereof are shown in Table 2.

Example 2 of Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 1 ofInvention 2, except that in the preparation of a nonaqueous electrolyte,the amount of heptane was changed from 2% by mass to 0.5% by mass . Theresults thereof are shown in Table 2.

Example 3 of Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 1 ofInvention 2, except that in the preparation of a nonaqueous electrolyte,2% by mass cyclohexane was used in place of the 2% by mass heptane. Theresults thereof are shown in Table 2.

Example 4 of Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 3 ofInvention 2, except that in the preparation of a nonaqueous electrolyte,the amount of cyclohexane was changed from 2% by mass to 0.5% by mass.The results thereof are shown in Table 2.

Example 5 of Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 1 ofInvention 2, except that in the preparation of a nonaqueous electrolyte,2% by mass fluorobenzene was used in place of the 2% by mass heptane.The results thereof are shown in Table 2.

Example 6 of Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 5 ofInvention 2, except that in the preparation of a nonaqueous electrolyte,the amount of fluorobenzene was changed from 2% by mass to 0.5% by mass.The results thereof are shown in Table 2.

Example 7 of Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 1 ofInvention 2, except that in the preparation of a nonaqueous electrolyte,2% by mass nonafluorobutyl ethyl ether was used in place of the 2% bymass heptane. The results thereof are shown in Table 2.

Example 8 of Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 7 ofInvention 2, except that in the preparation of a nonaqueous electrolyte,the amount of nonafluorobutyl ethyl ether was changed from 2% by mass to0.5% by mass. The results thereof are shown in Table 2.

Example 9 of Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 3 ofInvention 2, except that in the preparation of a nonaqueous electrolyte,0.2% by mass sodium difluorophosphate was used in place of the 0.2% bymass lithium difluorophosphate. The results thereof are shown in Table2.

Comparative Example 1 for Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 1 ofinvention 2, except that in the preparation of a nonaqueous electrolyte,neither the compound among the compounds of invention 2 nor the lithiumdifluorophosphate was used. The results thereof are shown in Table 2.

Comparative Example 2 for Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 1 ofinvention 2, except that in the preparation of a nonaqueous electrolyte,the lithium difluorophosphate was not used. The results thereof areshown in Table 2.

Comparative Example 3 for Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 3 ofinvention 2, except that in the preparation of a nonaqueous electrolyte,the lithium difluorophosphate was not used. The results thereof areshown in Table 2.

Comparative Example 4 for Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 5 ofinvention 2, except that in the preparation of a nonaqueous electrolyte,the lithium difluorophosphate was not used. The results thereof areshown in Table 2.

Comparative Example 5 for Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 7 ofinvention 2, except that in the preparation of a nonaqueous electrolyte,the lithium difluorophosphate was not used. The results thereof areshown in Table 2.

Comparative Example 6 for Invention 2

A nonaqueous-electrolyte secondary battery was produced and subjected tothe battery characteristics test in the same manners as in Example 7 ofinvention 2, except that in the preparation of a nonaqueous electrolyte,the compound among the compounds of invention 2 was not used. Theresults thereof are shown in Table 2.

In Table 2 are shown the proportions of the initial output and outputafter cycling of each battery to the initial output and output aftercycling of the battery of Comparative Example 1 for invention 2 whichare taken as 100%.

TABLE 2 Compound in the Monofluorophosphate and/ Output after cyclingcompounds of invention or difluorophosphate Initial output (%) (%)Example 1 Heptane   2% lithium difluorophosphate 0.2% 128 133 Example 2Heptane 0.5% lithium difluorophosphate 0.2% 126 131 Example 3Cyclohexane   2% lithium difluorophosphate 0.2% 132 138 Example 4Cyclohexane 0.5% lithium difluorophosphate 0.2% 128 133 Example 5Fluorobenzene   2% lithium difluorophosphate 0.2% 126 132 Example 6Fluorobenzene 0.5% lithium difluorophosphate 0.2% 124 130 Example 7nonafluorobutyl ethyl ether   2% lithium difluorophosphate 0.2% 130 135Example 8 nonafluorobutyl ethyl ether 0.5% lithium difluorophosphate0.2% 127 132 Example 9 Cyclohexane   2% sodium difluorophosphate 0.2%127 133 Comparative Example 1 none none 100 100 Comparative Example 2Heptane   2% none 100 100 Comparative Example 3 Cyclohexane   2% none100 101 Comparative Example 4 Fluorobenzene   2% none 99 100 ComparativeExample 5 nonafluorobutyl ethyl ethe   2% none 100 101 ComparativeExample 6 none lithium difluorophosphate 0.2% 121 124

As apparent from Table 2, the following was found. Thenonaqueous-electrolyte secondary batteries of Example 1 to Example 9 ofinvention 2, which employed nonaqueous electrolytes each containing botha compound belonging to the compounds of invention 2 and adifluorophosphate, had higher output characteristics than thenonaqueous-electrolyte secondary battery of Comparative Example 6 forinvention 2, which contained lithium difluorophosphate only, not tomention the nonaqueous-electrolyte secondary battery of ComparativeExample 1 for invention 2, which contained neither of the twoingredients. Furthermore, a comparison in output after thehigh-temperature cycling revealed that the batteries of Example 1 toExample 9 of invention 2 each had a large increase in output based onthe output in Comparative Example 1 for invention 2.

On the other hand, a comparison between Comparative Example 2 toComparative Example 5 for invention 2, in which the nonaqueouselectrolytes each contained a compound belonging to the compounds ofinvention 2 but contained no difluorophosphate, and thenonaqueous-electrolyte secondary battery of Comparative Example 1 forinvention 2, which contained neither of the two ingredients, revealedthat the compounds belonging to the compounds of invention 2 exertedalmost no influence on output. Those results clearly show the usefulnessof invention 2 which resides in that output characteristics are improvedby using a compound belonging to the compounds of invention 2 incombination with lithium difluorophosphate.

[With Respect to Invention 3] Example 1 of Invention 3 <Production ofSecondary Battery> [Production of Positive Electrode]

Ninety-four percents by mass lithium cobalt oxide (LiCoO₂) as apositive-electrode active material was mixed with 3% by mass acetyleneblack as a conductive material and 3% by mass poly(vinylidene fluoride)(PVdF) as a binder in N-methylpyrrolidone solvent to prepare a slurry.The slurry obtained was applied to each side of an aluminum foil havinga thickness of 14 μm and dried. The coated foil was rolled with apressing machine to a thickness of 85 μm. A disk having a diameter of12.5 mm was punched out of the coated foil to obtain a positiveelectrode.

[Production of Negative Electrode]

An electrolytic copper foil having a thickness of 18 μm was used as acurrent collector base. This foil was subjected to the deposition of athin silicon film thereon using a DC sputtering apparatus (“HSM-52”,manufactured by Shimadzu Corp.) and silicon as a target material underthe conditions of a power density of 4.7 W/cm² and a deposition rate(film formation rate) of about 1.8 nm/sec. Thus, a silicon-thin-filmnegative electrode was obtained.

[Nonaqueous Electrolyte]

In a dry argon atmosphere, LiPF₆ and a difluorophosphate which each hadbeen sufficiently dried were dissolved, in concentrations of 1 mol/L and1% by mass, respectively, in a mixture of ethylene carbonate and diethylcarbonate (volume ratio, 3:7) to obtain a desired nonaqueouselectrolyte.

[Treatment of Electrode]

The negative electrode obtained above was treated in the followingmanner. 3-Methacrylopropyltriethoxysilane was dissolved in diethylcarbonate (DEC) so as to result in a concentration thereof of 1% by massbased on the DEC to prepare a negative-electrode treatment liquid. Theelectrode was immersed in this negative-electrode treatment liquid andthen heat-treated at 110° C. for 1 hour. Thereafter, the electrode wasvacuum-dried at 60° C. for 11 hours and then used. On the other hand,the positive electrode was vacuum-dried at 80° C. for 11 hours, withoutbeing subjected to that treatment, and then used.

[Production of Nonaqueous-Electrolyte Secondary Battery]

The positive electrode was placed in a stainless-steel can serving alsoas a positive-electrode conductor, and the negative electrode was placedthereon through a separator which was made of polyethylene and had beenimpregnated with the electrolyte. This can was sealed together with acover plate serving also as a negative-electrode conductor by caulkingthrough a gasket for insulation. Thus, a coin cell was produced.

<Evaluation of Battery>

The battery was subjected to 5 cycles of charge/discharge at 25° C. anda constant current corresponding to 0.2 C under the conditions of afinal charge voltage of 4.2 V and a final discharge voltage of 2.5 V tostabilize battery operation. In the 6th cycle, the battery was subjectedto 4.2-V constant-current constant-voltage charge (CCCV charge), inwhich the battery was charged to a final charge voltage of 4.2 V at acurrent corresponding to 0.2 C until the charge current reached a valuecorresponding to 0.02 C (0.02 C cutting), and then subjected to 2.5-Vdischarge at a constant current value corresponding to 0.5 C. In the 7thcycle, the battery was subjected to 4.2-V constant-currentconstant-voltage charge (CCCV charge) at a current corresponding to 0.20(0.02 C cutting) and then subjected to 2.5-V discharge at a constantcurrent corresponding to 1.0 C. Thereafter, the battery was subjected to92 cycles under such conditions that the battery was subjected to 4.2-Vconstant-current constant-voltage charge (CCCV charge) at a currentcorresponding to 0.50 (0.05 C cutting) and then subjected to 2.5-Vdischarge at a constant current value corresponding to 0.5 C. In the100th cycle, the battery was subjected to 4.2-V constant-currentconstant-voltage charge (CCCV charge) at a current corresponding to 0.2C (0.02 C cutting) and then subjected to 2.5-V discharge at a constantcurrent value corresponding to 0.20. “1 C” means a current value atwhich the battery can be fully charged by 1-hour charge.

Example 2 of Invention 3 to Example 4 of Invention 3

A positive electrode, negative electrode, and nonaqueous electrolytewere produced or prepared in the same manners as in Example 1 ofinvention 3. Subsequently, the electrodes were treated in each Examplein the following manners. As shown in Table 3, diethyl carbonate (DEC)or pure water was used in each Example, and3-methacrylopropyltriethoxysilane or 3-aminopropyltriethoxysilane wasdissolved or dispersed therein so as to result in a concentration of 1%by mass based on the DEC or water. Thus, negative-electrode treatmentliquids for the respective Examples were prepared. The negativeelectrode was treated in the same manner as in Example 1 of invention 3.The treatment of the positive electrode was also conducted in the samemanner as in Example 1 of invention 3. Nonaqueous-electrolyte secondarybatteries were produced in the same manner as in Example 1 of invention3. Thereafter, battery evaluation was conducted in the same manner as inExample 1 of invention 3. The results thereof are also shown in Table 3.

Comparative Example 1 for Invention 3

A nonaqueous electrolyte was prepared in the same manner as in Example 1of invention 3, except that lithium difluorophosphate was not used.Furthermore, a positive electrode and a negative electrode were producedin the same manners as in Example 1 of invention 3. Subsequently, thenegative electrode was subjected only to 11-hour vacuum drying at 60° C.The treatment of the positive electrode was conducted in the same manneras in Example 1 of invention 3. A nonaqueous-electrolyte secondarybattery was produced in the same manner as in Example 1 of invention 3.Thereafter, battery evaluation was conducted in the same manner as inExample 1 of invention 3. The results thereof are also shown in Table 3.

Comparative Example 2 to Comparative Example 5 for Invention

A nonaqueous electrolyte was prepared in the same manner as in Example 1of invention 3, except that lithium difluorophosphate was not used.Furthermore, a positive electrode and a negative electrode were producedin the same manners as in Example 1 of invention 3. Subsequently,electrode treatments were conducted in the following manner. As shown inTable 3, diethyl carbonate (DEC) or pure water was used in eachComparative Example, and 3-methacrylopropyltriethoxysilane or3-aminopropyltriethoxysilane was dissolved or dispersed therein so as toresult in a concentration of 1% by mass based on the DEC or water. Thus,negative-electrode treatment liquids for the respective ComparativeExamples were prepared. The negative electrode was treated in the samemanner as in Example 1 of invention 3. The treatment of the positiveelectrode was also conducted in the same manner as in Example 1 ofinvention 3. Nonaqueous-electrolyte secondary batteries were produced inthe same manner as in Example 1 of invention 3. Thereafter, batteryevaluation was conducted in the same manner as in Example 1 of invention3. The results thereof are also shown in Table 3.

Comparative Example 6 for Invention 3

A positive electrode, negative electrode, and nonaqueous electrolytewere produced or prepared in the same manners as in Example 1 ofinvention 3. Subsequently, the negative electrode was subjected only to11-hour vacuum drying at 60° C. The treatment of the positive electrodewas conducted in the same manner as in Example 1 of invention 3. Anonaqueous-electrolyte secondary battery was produced in the same manneras in Example 1 of invention 3. Thereafter, battery evaluation wasconducted in the same manner as in Example 1 of invention 3. The resultsthereof are also shown in Table 3.

It was ascertained by gas chromatography that after the production ofthe nonaqueous-electrolyte secondary batteries of Example 1 of invention3, Example 2 of invention 3, and Comparative Example 2 and ComparativeExample 3 for invention 3, the nonaqueous electrolyte in each batterycontained 3-methacrylopropyltriethoxysilane in an amount of 0.06% bymass based on the whole nonaqueous electrolyte. It was furtherascertained by gas chromatography that after the production of thenonaqueous-electrolyte secondary batteries of Example 3 of invention 3,Example 4 of invention 3, and Comparative Example 4 and ComparativeExample 5 for invention 3, the nonaqueous electrolyte in each batterycontained 3-aminopropyltriethoxysilane in an amount of 0.13% by massbased on the whole nonaqueous electrolyte.

With respect to the results, the ratio of the discharge capacity of eachbattery as measured in the 50th cycle to the discharge capacity asmeasured in the 50th cycle of the battery of Comparative Example 1 (nonegative-electrode treatment; no difluorophosphate) for invention 3 isshown as “50th-cycle discharge capacity ratio” in Table 3. Namely, the“50th-cycle discharge capacity ratio” is expressed by (50th-cycledischarge capacity ratio)=(discharge capacity in 50th cycle)/(dischargecapacity in 50th cycle in Comparative Example 1 for invention 3).

TABLE 3 50th-cycle Difluorophosphate discharge Negative-electrodetreatment liquid (mass %) capacity ratio Example 13-methacrylopropyltriethoxysilane lithium difluorophosphate 1.24 (1% DECsolution) (1) Example 2 3-methacrylopropyltriethoxysilane lithiumdifluorophosphate 1.24 (1% H₂O solution) (1) Example 33-aminopropyltriethoxysilane lithium difluorophosphate 1.22 (1% DECsolution) (1) Example 4 3-aminopropyltriethoxysilane lithiumdifluorophosphate 1.27 (1% H₂O solution) (1) Comparative Example 1 nonenone 1 Comparative Example 2 3-methacrylopropyltriethoxysilane none 1.15(1% DEC solution) Comparative Example 33-methacrylopropyltriethoxysilane none 1.06 (1% H₂O solution)Comparative Example 4 3-aminopropyltriethoxysilane none 1.17 (1% DECsolution) Comparative Example 5 3-aminopropyltriethoxysilane none 1.08(1% H₂O solution) Comparative Example 6 none lithium difluorophosphate1.19 (1)

As apparent from Table 3, the nonaqueous-electrolyte secondary batteriesemploying a negative electrode treated with a compound represented bygeneral formula (1) or general formula (2) (requirement 1) and producedusing a nonaqueous electrolyte of invention 3 which contained lithiumdifluorophosphate as the “monofluorophosphate and/or difluorophosphate”(requirement 2) showed larger values of discharge capacity after 50cycles than the nonaqueous-electrolyte secondary batteries whichsatisfied only either of requirement 1 and requirement 2 or satisfiedneither of the requirements. These secondary batteries according toinvention 3 were able to be inhibited from deteriorating withcharge/discharge and to have a prolonged battery life.

Specifically, the batteries of Example 1 to Example 4 of invention 3,which satisfied both requirement 1 and requirement 2, were inhibitedfrom deteriorating in battery characteristics with charge/discharge. Incontrast, the battery of Comparative Example 1 for invention 3, whichsatisfied neither of the requirements, was found to have a low dischargecapacity retention and deteriorate considerably. The batteries ofComparative Example 2 to Comparative Example 6 for invention 3, whichsatisfied only either of requirement 1 and requirement 2, each showed ahigh discharge capacity as compared with Comparative Example 1 forinvention 3. The effect of inhibiting battery deterioration therein wasascertained. However, this effect was low as compared with that in thenonaqueous-electrolyte secondary batteries of invention 3 (Example 1 toExample 4 of invention 3). Although the expressions “requirement 1” and“requirement 2” were used above, the requirements should not beconstrued as being limited to the contents of those Examples ofinvention 3 so long as the contents of the claims are satisfied.

[With Respect to Invention 4] [Preparation of Electrolyte]

In a dry argon atmosphere, 151.9 g of sufficiently dried lithiumhexafluorophosphate (LiPF₆) was dissolved in a solvent prepared bymixing purified ethylene carbonate/purified dimethyl carbonate/purifiedethyl methyl carbonate in amounts of 381.6 g/310.0 g/391.5 g (about 290mL/290 mL/385 mL), respectively. This solution had a specific gravity of1.22. One or more additives were added to the solution in the amountsshown in Table 4, and dissolved therein.

TABLE 4 Monofluorophosphate, Compound represented by difluorophosphate,or general formula (3) specific carbonic acid ester Amount AmountInvention Electrolyte Kind (mass %/vol %) Kind [mass %] embodiment 1Compound A 0.50/0.20 vinylene carbonate 0.5 2 2 Compound A 1.00/0.39vinylene carbonate 0.5 2 3 Compound A 0.50/0.20 vinylene carbonate 1 2 4Compound A 0.50/0.20 4-fluoro-1,3-dioxolan-2-one 1 2 5 Compound A0.50/0.20 lithium difluorophosphate 0.5 1 6 Compound A 0.50/0.20 lithiumdifluorophosphate 1 1 7 Compound A 1.00/0.39 lithium difluorophosphate0.5 1 8 Compound A 1.00/0.39 lithium difluorophosphate 1 1 9 Compound B0.50/0.26 lithium difluorophosphate 0.5 1 10  Compound A 0.50/0.204-fluoro-1,3-dioxolan-2-one 1 1 lithium difluorophosphate 1 11  CompoundA 0.50/0.20 vinylene carbonate 10 2 12  Compound A 5.00/1.95 vinylenecarbonate 0.5 2 A — — — — — B — — vinylene carbonate 10 — C — — lithiumdifluorophosphate 0.5 — D — — Compound C 0.5 — vinylene carbonate 0.5

In Table 4, “invention embodiment 1” indicates “embodiment 4-1” and“invention embodiment 2” indicates “embodiment 4-2”. “Compoundrepresented by general formula (3)” indicates “compound represented bygeneral formula (3) in invention 4”.

[Production of Secondary Batteries] <Production of “Secondary Battery1″> (Production of Positive Electrode)

90% by mass lithium cobalt oxide (LiCoO₂) as a positive-electrode activematerial was mixed with 5% by mass acetylene black as a conductivematerial and 5% by mass poly(vinylidene fluoride) (hereinafterabbreviated to “PVDF”) as a binder in N-methylpyrrolidone solvent toprepare a slurry. The slurry obtained was applied to each side of a15-μm aluminum foil and dried. The coated foil was rolled with apressing machine to a thickness of 80 μm. A piece which included anactive-material layer size having a width of 100 mm and a length of 100mm and had an uncoated part having a width of 30 mm was cut out of thecoated foil. Thus, a positive electrode was obtained.

(Production of Negative Electrode)

To 98 parts by mass of artificial-graphite powder KS-44 (trade name;manufactured by Timcal) were added 100 parts by mass of an aqueousdispersion of sodium carboxymethyl cellulose (concentration of sodiumcarboxymethyl cellulose, 1% by mass) as a thickener and 2 parts by massof an aqueous dispersion of a styrene/butadiene rubber (concentration ofstyrene/butadiene rubber, 50% by mass) as a binder. The ingredients weremixed together by means of a disperser to obtain a slurry.

The slurry obtained was applied to each side of a 10-μm copper foil anddried. The coated foil was rolled with a pressing machine to a thicknessof 75 μm. Apiece which included an active-material layer size having awidth of 104 mm and a length of 104 mm and had an uncoated part having awidth of 30 mm was cut out of the coated foil. Thus, a negativeelectrode was obtained.

(Battery Assembly)

The positive electrode and the negative electrode were superposedtogether with separators made of polyethylene in order to prevent thepositive electrode and negative electrode from coming into directcontact with each other. This assemblage was wound to obtain anelectrode structure. This electrode structure was placed in a batterycan so that the terminals of the positive electrode and negativeelectrode protruded outside. Subsequently, 5 mL of the electrolyte whichwill be described later was introduced into the battery can, which wasthen caulked to produce a cylindrical battery of the 18650 type. Thisbattery is referred to as “secondary batter 1”.

<Production of “Secondary Battery 2”>

A battery was produced in the same manner as for secondary battery 1,except that a lithium-nickel-manganese-cobalt oxide(LiNi_(1/3)Mn_(1/3)Co_(1/3)O₂) was used as a positive-electrode activematerial in place of the lithium cobalt oxide, and that the chargevoltage was changed to 4.25 V. This battery is referred to as “secondarybattery 2”.

<Production of “Secondary Battery 3”>

A battery was produced in the same manner as for secondary battery 1,except that lithium iron oliphinate (LiFePO₄) was used as apositive-electrode active material in place of the lithium cobalt oxide,and that the charge voltage was changed to 4.25 V. This battery isreferred to as “secondary battery 3”.

<Production of “Secondary Battery 4”>

As negative-electrode active materials, use was made of 73.2 parts bymass of silicon and 8.1 parts by mass of copper, which are non-carbonmaterials, and 12.2 parts by mass of an artificial-graphite powder(trade name “KS-6”, manufactured by Timcal). Thereto were added 54.2parts by mass of an N-methylpyrrolidone solution containing 12% by massPVDF and 50 parts by mass of N-methylpyrrolidone. These ingredients weremixed together by means of a disperser to obtain slurry.

The slurry obtained was evenly applied to a copper foil having athickness of 18 μm as a negative-electrode current collector. Thecoating was first allowed to dry naturally and finally vacuum-dried at85° C. for a whole day and night. Thereafter, the coated foil waspressed so as to result in an electrode density of about 1.5 g·cm⁻³. Adisk having a diameter of 12.5 mm was punched out of the coated foil toobtain a negative electrode (silicon-alloy negative electrode). Exceptfor the procedure described above, a battery was produced in the samemanner as for secondary battery 1. This battery is referred to as“secondary battery 4”.

<Production of “Secondary Battery 5”>

Ninety percents by mass negative-electrode active material(Li_(4/3)Ti_(5/3)O₄) was mixed with 5% by mass acetylene black as aconductive material and 5% by mass poly(vinylidene fluoride) (PVdF) as abinder in N-methylpyrrolidone solvent to obtain a slurry.

The slurry obtained was applied to one side of a 10-μm rolled copperfoil and dried. The coated foil was rolled with a pressing machine to 90μm. A piece which included an active-material layer size having a widthof 104 mm and a length of 104 mm and had an uncoated part having a widthof 30 mm was cut out of the coated foil to obtain a negative electrode.Except for the procedure described above, a battery was produced in thesame manner as for secondary battery 1. This battery is referred to as“secondary battery 5”.

Examples 1 to 14 of Invention 4 and Comparative Examples 1 to 8 forInvention 4

In Examples 1 to 14 of invention 4 and Comparative Examples 1 to 8 forinvention 4, experiments were made respectively for the Examples ofinvention 4 and Comparative Examples for invention 4 using thecombinations of experimental conditions (kinds of electrolyte andsecondary battery) given in the following Table 5 and Table 6. Resultswere obtained with respect to the evaluation items described below.These results also are shown in Table 5 and Table 6.

[Evaluation of Secondary Batteries]

The secondary batteries were evaluated respectively under the followingconditions. <Evaluation of Secondary Battery 1>

(Initial Capacity)

At 25° C., the battery was charged to 4.2 V by the constant-currentconstant-voltage charging method at 0.2 C and then discharged to 3.0 Vat a constant current of 0.2 C. This operation as one cycle was repeatedto conduct 5 cycles and thereby stabilize the battery. The dischargecapacity as measured in the fifth cycle is referred to as “initialcapacity”. Incidentally, the current value at which rated capacity isdischarged over 1 hour is referred to as 1 C.

(Capacity Retention Through Cycling)

At 60° C., the battery which had undergone the initial charge/dischargewas subjected to 500 cycles of charge/discharge in each of which thebattery was charged to 4.2 V by the constant-current constant-voltagemethod at 1 C and then discharged to 3.0 V at a constant current of 1 C.The proportion of the 500th-cycle discharge capacity to the 1st-cycledischarge capacity both measured in this operation is referred to as“capacity retention through cycling”.

(Initial Low-Temperature Discharge Rate)

The battery which had undergone the initial charge/discharge was chargedto 4.2 V at 25° C. by the constant-current constant-voltage chargingmethod at 0.2 C and then subjected at −30° C. to constant-currentdischarge at 0.2 C. The discharge capacity as measured in this dischargeis referred to as initial low-temperature capacity, and the proportionof the initial low-temperature capacity to the initial capacity isreferred to as “initial low-temperature discharge rate”.

(Low-Temperature Discharge Rate After Cycling)

At 25° C., the battery which had undergone the cycle test was charged to4.2 V by the constant-current constant-voltage method at 0.2 C and thendischarged to 3.0 V at a constant current of 0.2 C. This operation asone cycle was repeated to conduct three cycles. The discharge capacityas measured in the 3rd cycle is referred to as capacity after cycling.Thereafter, the same battery was charged to 4.2 V at 25° C. by theconstant-current constant-voltage charging method at 0.2 C and thensubjected at −30° C. to constant-current discharge at 0.2 C. Thedischarge capacity as measured in this discharge is referred to aslow-temperature capacity after cycling, and the proportion of thelow-temperature capacity after cycling to the capacity after cycling isreferred to as “low-temperature discharge rate after cycling.”

<Evaluation of Secondary Battery 2>

The battery was evaluated for the same items as in the evaluation ofsecondary battery 1 in the same manners as in the evaluation, exceptthat the charge voltage in each test was changed from 4.2 V to 4.25 V.

<Evaluation of Secondary Battery 3>

The battery was evaluated for the same items as in the evaluation ofsecondary battery 1 in the same manners as in the evaluation, exceptthat the charge voltage in each test was changed from 4.2 V to 3.8 V andthe discharge voltage in each test was changed from 3.0 V to 2.5 V.

<Evaluation of Secondary Battery 4>

The battery was evaluated for the same items as in the evaluation ofsecondary battery 1 in the same manners as in the evaluation, exceptthat the discharge voltage in each test was changed from 3.0 V to 2.5 V.

<Evaluation of Secondary Battery 5>

The battery was evaluated for the same items as in the evaluation ofsecondary battery 1 in the same manners as in the evaluation, exceptthat the charge voltage in each test was changed from 4.2 V to 2.7 V andthe discharge voltage in each test was changed from 3.0 V to 1.9 V.

In Examples 1 to 16 of invention 4, in which electrolytes 1 to 12 wereemployed, the batteries were excellent in all of initial capacity,capacity retention through cycling, initial low-temperature dischargerate, and low-temperature discharge rate after cycling. In contrast, inComparative Examples 1 to 8 for invention 4, in which electrolytes A toD were employed, the batteries were inferior in at least one of thoseitems.

TABLE 5 Capacity retention Initial Low-temperature throughlow-temperature discharge rate Initial capacity cycling discharge rateafter cycling No. Electrolyte Battery [mA] [%] [%] [%] Example 1 1secondary 700 74 65 63 battery 1 Example 2 2 secondary 700 75 66 65battery 1 Example 3 3 secondary 703 78 63 63 battery 1 Example 4 4secondary 701 76 68 66 battery 1 Example 5 5 secondary 700 68 71 69battery 1 Example 6 6 secondary 700 70 73 72 battery 1 Example 7 7secondary 700 70 72 71 battery 1 Example 8 8 secondary 700 71 75 73battery 1 Example 9 9 secondary 700 68 68 67 battery 1 Example 10 10secondary 700 77 75 74 battery 1 Example 11 11 secondary 700 78 56 54battery 1 Example 12 12 secondary 680 78 65 63 battery 1 Comparative Asecondary 700 64 61 54 Example 1 battery 1 Comparative B secondary 70174 59 56 Example 2 battery 1 Comparative C secondary 700 66 68 65Example 3 battery 1 Comparative D secondary 690 60 50 48 Example 4battery 1

TABLE 6 Capacity Initial Low-temperature retention low-temperaturedischarge rate Initial capacity through cycling discharge rate aftercycling No. Electrolyte Battery [mA] [%] [%] [%] Example 13 1 secondary755 70 65 64 battery 2 Comparative A secondary 750 60 62 56 Example 5battery 2 Example 14 1 secondary 727 65 60 55 battery 3 Comparative Asecondary 725 57 55 49 Example 6 battery 3 Example 15 1 secondary 701 5870 65 battery 4 Comparative A secondary 700 50 65 58 Example 7 battery 4Example 16 1 secondary 725 89 96 92 battery 5 Comparative A secondary725 85 92 88 Example 8 battery 5

[With Respect to Invention 5]

The batteries obtained in the following Examples and ComparativeExamples each were evaluated by the method shown below.

[Evaluation of Discharge Capacity]

At 60° C., the nonaqueous-electrolyte battery was charged to 4.2 V at aconstant current corresponding to 0.1 C and then discharged to 3 Vat aconstant current of 0.1 C. This operation as one cycle was repeated toconduct 20 cycles. The proportion of the discharge capacity after the 20cycles (%) to the initial discharge capacity which was taken as 100 wasdetermined. This proportion is referred to as “discharge capacity aftercycling (%)”. “1 C” means the current value at which the referencecapacity of a battery is discharged over 1 hour; “0.1 C” means thecurrent value which is 1/10 that current value.

Example 1 of Invention 5 [Production of Nonaqueous Electrolyte]

In a dry argon atmosphere, sufficiently dried lithiumbis(trifluoromethanesulfonyl)imide (hereinafter abbreviated to “LiTFSI”)was dissolved in N-butyl-N-methylpyrrolidiniumbis(trifluoromethanesulfonyl)imide (hereinafter abbreviated to“BMPTFSI”) so as to result in a proportion thereof of 0.4 mol/L.Furthermore, sufficiently dried lithium difluorophosphate (hereinaftersometimes referred to as “LiPO₂F₂”) was dissolved therein in an amountof 2 parts by weight per 98 parts by weight of the mixture of BMPTFSIand LiTFSI. Thus, a nonaqueous electrolyte was obtained.

[Production of Nonaqueous-Electrolyte Battery]

Ninety percents by mass lithium cobalt oxide (LiCoO₂) as apositive-electrode active material was mixed with 5% by mass acetyleneblack as a conductive material and 5% by mass poly(vinylidene fluoride)(PVdF) as a binder in N-methylpyrrolidone solvent to obtain a slurry.The slurry obtained was applied to one side of an aluminum foil having athickness of 15 μm and dried. The coated foil was rolled with a pressingmachine to a thickness of 80 μm. A disk having a diameter of 12.5 mm interms of active-material layer size was punched out of the coated foilto produce an electrode. This electrode as a working electrode was usedtogether with a lithium foil as a counter electrode and a separatorimpregnated with the nonaqueous electrolyte and interposed between theelectrodes. Thus, a nonaqueous-electrolyte battery which was a coin typelithium secondary battery was produced. This battery was evaluated. Thecomponents of the nonaqueous electrolyte are shown in Table 7, and theresults of the evaluation are shown in Table 8.

Example 2 of Invention 5

A coin type lithium secondary battery was produced and evaluated in thesame manners as in Example 1 of invention 5, except thatN-butyl-N,N,N-trimethylammonium bis(trifluoromethanesulfonyl)imide(hereinafter abbreviated to “BTMATFSI”) was used in place of the BMPTFSIused in the nonaqueous electrolyte of Example 1 of invention 5. Thecomponents of the nonaqueous electrolyte are shown in Table 7, and theresults of the evaluation are shown in Table 8.

Example 3 of Invention 5

A coin type lithium secondary battery was produced and evaluated in thesame manners as in Example 1 of invention 5, except thatN,N-dimethyl-N-methyl-N-methoxyethylammoniumbis(trifluoromethanesulfonyl)imide (hereinafter abbreviated to“DEMETFSI”) was used in place of the BMPTFSI used in the nonaqueouselectrolyte of Example 1 of invention 5. The components of thenonaqueous electrolyte are shown in Table 7, and the results of theevaluation are shown in Table 8.

Comparative Example 1 for Invention 5

A coin type lithium secondary battery was produced and evaluated in thesame manners as in Example 1 of invention 5, except that use was made ofa nonaqueous electrolyte produced by dissolving sufficiently driedLiTFSI in BMPTFSI so as to result in a proportion thereof of 0.4 mol/L.The components of the nonaqueous electrolyte are shown in Table 7, andthe results of the evaluation are shown in Table 8.

Comparative Example 2 for Invention 5

A coin type lithium secondary battery was produced and evaluated in thesame manners as in Example 1 of invention 5, except that use was made ofa nonaqueous electrolyte produced by dissolving sufficiently driedLiTFSI in BTMATFSI so as to result in a proportion thereof of 0.4 mol/L.The components of the nonaqueous electrolyte are shown in Table 7, andthe results of the evaluation are shown in Table 8.

Comparative Example 3 for Invention 5

A coin type lithium secondary battery was produced and evaluated in thesame manners as in Example 1 of invention 5, except that use was made ofa nonaqueous electrolyte produced by dissolving sufficiently driedLiTFSI in DEMETFSI so as to result in a proportion thereof of 0.4 mol/L.The components of the nonaqueous electrolyte are shown in Table 7, andthe results of the evaluation are shown in Table 8.

TABLE 7 Lithium Ambient-temperature- No. salt molten salt LiPO₂F₂Example 1 LiTFSI BMPTFSI 2 mass % Example 2 LiTFSI BTMATFSI 2 mass %Example 3 LiTFSI DEMETFSI 2 mass % Comparative Example 1 LiTFSI BMPTFSI— Comparative Example 2 LiTFSI BTMATFSI — Comparative Example 3 LiTFSIDEMETFSI —

TABLE 8 No. Discharge capacity after cycling (%) Example 1 91.2 Example2 90.8 Example 3 92.5 Comparative Example 1 32.4 Comparative Example 265.9 Comparative Example 3 69.5

As apparent from the results given in Table 8, the batteries employingnonaqueous electrolytes according to invention 5 (Examples 1 to 3 ofinvention 5) had high charge/discharge characteristics. In contrast, thebatteries employing nonaqueous electrolytes which were outside the rangeof invention 5 (Comparative Examples 1 to 3 for invention 5) had poorcharge/discharge characteristics.

INDUSTRIAL APPLICABILITY

According to the nonaqueous electrolyte of invention 1, anonaqueous-electrolyte secondary battery having high capacity andexcellent cycle performances can be produced. The electrolyte and thebattery are hence suitable for use in all fields wherenonaqueous-electrolyte secondary batteries are used, e.g., in the fieldof electronic appliances.

Applications of the nonaqueous electrolyte and nonaqueous-electrolytesecondary battery of invention 1 are not particularly limited, and theelectrolyte and battery can be used in various known applications.Examples thereof include notebook personal computers, pen-input personalcomputers, mobile personal computers, electronic-book players, portabletelephones, portable facsimile telegraphs, portable copiers, portableprinters, headphone stereos, video movie cameras, liquid-crystal TVs,handy cleaners, portable CD players, mini-disk players, transceivers,electronic pocketbooks, electronic calculators, memory cards, portabletape recorders, radios, backup power sources, motors, motor vehicles,motorbikes, bicycles fitted with a motor, bicycles, illuminators, toys,game machines, clocks and watches, power tools, stroboscopes, andcameras.

According to the nonaqueous electrolyte of invention 2, anonaqueous-electrolyte secondary battery excellent not only in outputcharacteristics but in high-temperature storability and cycleperformances can be produced. The electrolyte and the battery are hencesuitable for use in all fields where nonaqueous-electrolyte secondarybatteries are used, e.g., in the field of electronic appliances.

Applications of the nonaqueous electrolyte and nonaqueous-electrolytesecondary battery of invention 2 are not particularly limited, and theelectrolyte and battery can be used in various known applications.Examples of the applications include those enumerated above with regardto invention 1.

According to the nonaqueous electrolyte of invention 3, a nonaqueouselectrolyte and a nonaqueous-electrolyte secondary battery can beprovided which have excellent cycle performances. The electrolyte andthe battery are hence suitable for use in various fields wherenonaqueous-electrolyte secondary batteries are used, e.g., in the fieldof electronic appliances.

Applications of the nonaqueous electrolyte for secondary batteries andthe nonaqueous-electrolyte secondary battery of invention 3 are notparticularly limited, and the electrolyte and battery can be used invarious known applications. Examples of the applications include thoseenumerated above with regard to invention 1.

The lithium secondary battery employing the nonaqueous electrolyte ofinvention 4 is excellent in low-temperature discharge characteristicsand heavy-current discharge characteristics and also in high-temperaturestorability and cycle performances. The electrolyte and the battery arehence suitable for use in all fields where secondary batteries are used,e.g., in the field of electronic appliances. Examples of applicationsinclude those enumerated above with regard to invention 1.

The nonaqueous-electrolyte battery employing the nonaqueous electrolyteof invention 5 retains high capacity and is excellent in safety, etc.The electrolyte and the battery can hence be used in various knownfields. Examples of applications include those enumerated above withregard to invention 1.

This application is based on the following Japanese patent applications,the entire contents thereof being herein incorporated as a disclosure ofthe description of the invention.

Invention 1: Application No. 2007-111918 (filing date: Apr. 20, 2007)

Invention 1-1: Application No. 2008-267700 (filing date: Oct. 16, 2008)

Invention 2: Application No. 2007-111976 (filing date: Apr. 20, 2007)

Invention 3: Application No. 2007-116448 (filing date: Apr. 26, 2007)

Invention 4: Application No. 2007-272163 (filing date: Oct. 19, 2007)

Invention 5: Application No. 2007-116444 (filing date: Apr. 26, 2007)

1. A nonaqueous electrolyte comprising a nonaqueous solvent and anelectrolyte dissolved therein, wherein the nonaqueous electrolytecomprises a monofluorophosphate and/or a difluorophosphate and furthercomprises an iron-group element in an amount of 1-2,000 ppm based on thewhole nonaqueous electrolyte.
 2. The nonaqueous electrolyte according toclaim 1, wherein the iron-group element is cobalt element and/or nickelelement.
 3. The nonaqueous electrolyte according to claim 1 or claim 2,wherein the monofluorophosphate and/or difluorophosphate is adifluorophosphate.
 4. The nonaqueous electrolyte according to any one ofclaim 1 to claim 3, wherein the total content of the monofluorophosphateand/or difluorophosphate is from 0.001% by mass to 5% by mass based onthe whole nonaqueous electrolyte.
 5. A nonaqueous electrolyte mainlycomprising a nonaqueous solvent and an electrolyte dissolved therein,wherein the nonaqueous electrolyte comprises at least one compoundselected from the group consisting of saturated chain hydrocarbons,saturated cyclic hydrocarbons, aromatic compounds having a halogen atom,and ethers having a fluorine atom, and further comprises amonofluorophosphate and/or a difluorophosphate.
 6. The nonaqueouselectrolyte according to claim 5, wherein the at least one compoundselected from the group consisting of saturated chain hydrocarbons,saturated cyclic hydrocarbons, aromatic compounds having a halogen atom,and ethers having a fluorine atom is at least one saturated cyclichydrocarbon.
 7. The nonaqueous electrolyte according to claim 5, whereinthe at least one compound selected from the group consisting ofsaturated chain hydrocarbons, saturated cyclic hydrocarbons, aromaticcompounds having a halogen atom, and ethers having a fluorine atom isethers having a fluorine atom.
 8. The nonaqueous electrolyte accordingto any one of claim 5 to claim 7, wherein the at least one compoundselected from the group consisting of saturated chain hydrocarbons,saturated cyclic hydrocarbons, aromatic compounds having a halogen atom,and ethers having a fluorine atom is contained in an amount of 0.01-15%by mass based on the whole nonaqueous electrolyte.
 9. The nonaqueouselectrolyte according to any one of claim 5 to claim 8, wherein themonofluorophosphate and/or difluorophosphate is contained in a totalamount of from 0.001% by mass to 5% by mass based on the wholenonaqueous electrolyte.
 10. A nonaqueous electrolyte for secondarybattery which is a nonaqueous electrolyte for use in anonaqueous-electrolyte secondary battery comprising a negative electrodeand a positive electrode which are capable of occluding and releasingions and a nonaqueous electrolyte, wherein the nonaqueous electrolytecomprises an electrolyte and a nonaqueous solvent and further comprisesa monofluorophosphate and/or a difluorophosphate and a compoundrepresented by the following general formula (1) and/or the followinggeneral formula (2) in a proportion of from 0.001% by mass to 10% bymass based on the whole nonaqueous electrolyte:

[wherein R¹, R², R³, and R⁴ each independently are an organic group or ahalogen atom, provided that at least one of the R¹, R², R³, and R⁴ is agroup in which the atom directly bonded to the X is a heteroatom andthat two or more of the R¹, R², R³, and R⁴ may be the same; and X is anatom other than a carbon atom]

[wherein R⁵, R⁶, and R⁷ each independently are an organic group or ahalogen atom, provided that at least one of R⁵, R⁶, and R⁷ is a group inwhich the atom directly bonded to the Y is a heteroatom and that two ormore of the R⁵, R⁶, and R⁷ may be the same; and Y is an atom other thana carbon atom].
 11. A nonaqueous electrolyte for secondary battery whichis a nonaqueous electrolyte for use in a nonaqueous-electrolytesecondary battery comprising a negative electrode and a positiveelectrode which are capable of occluding and releasing ions and anonaqueous electrolyte, wherein the nonaqueous electrolyte comprises amonofluorophosphate and/or a difluorophosphate and is for use in thenonaqueous-electrolyte secondary battery in which the positive electrodeor negative electrode has been treated with a compound represented bythe following general formula (1) and/or the following general formula(2):

[wherein R¹, R², R³, and R⁴ each independently are an organic group or ahalogen atom, provided that at least one of the R¹, R², R³, and R⁴ is agroup in which the atom directly bonded to the X is a heteroatom andthat two or more of the R¹, R², R³, and R⁴ may be the same; and X is anatom other than a carbon atom]

[wherein R⁵, R⁶, and R⁷ each independently are an organic group or ahalogen atom, provided that at least one of R⁵, R⁶, and R⁷ is a group inwhich the atom directly bonded to the Y is a heteroatom and that two ormore of the R⁵, R⁶, and R⁷ may be the same; and Y is an atom other thana carbon atom].
 12. The nonaqueous electrolyte for secondary batteryaccording to claim 10 or claim 11, wherein X in the compound representedby general formula (1) is Si or Ti.
 13. The nonaqueous electrolyte forsecondary battery according to claim 10 or claim 11, wherein Y in thecompound represented by general formula (2) is Al.
 14. The nonaqueouselectrolyte for secondary battery according to any one of claim 10 toclaim 13, wherein the heteroatom directly bonded to the X or Y in thecompound represented by general formula (1) or general formula (2) is B,N, O, P, S, or a halogen atom.
 15. The nonaqueous electrolyte forsecondary battery according to any one of claim 10 to claim 14, whereinthe monofluorophosphate and/or difluorophosphate is contained in a totalamount of from 0.001% by mass to 5% by mass based on the wholenonaqueous electrolyte.
 16. A nonaqueous electrolyte comprising anonaqueous solvent and a lithium salt dissolved therein, wherein thenonaqueous electrolyte comprises a compound represented by the followinggeneral formula (3) and further comprises a monofluorophosphate and/or adifluorophosphate:

[wherein A and B each represent any of various substituents, providedthat at least one of the substituents represented by A and B isfluorine; and n is a natural number of 3 or larger].
 17. The nonaqueouselectrolyte according to claim 16, which further comprises a carbonicacid ester having at least one of an unsaturated bond and a halogenatom.
 18. The nonaqueous electrolyte according to claim 16 or claim 17,wherein the compound represented by general formula (3) is contained inan amount of from 0.001% by volume to 1% by volume based on the wholenonaqueous electrolyte.
 19. The nonaqueous electrolyte according to anyone of claim 16 to claim 18, wherein the monofluorophosphate and/ordifluorophosphate is contained in an amount of from 0.001% by mass to 5%by mass based on the whole nonaqueous electrolyte.
 20. The nonaqueouselectrolyte according to any one of claim 16 to claim 19, wherein thecarbonic acid ester having at least one of an unsaturated bond and ahalogen atom is contained in an amount of from 0.001% by mass to 5% bymass based on the whole nonaqueous electrolyte.
 21. A nonaqueouselectrolyte comprising a nonaqueous solvent and a lithium salt dissolvedtherein, wherein the nonaqueous electrolyte comprises: a compoundrepresented by the following general formula (3) in an amount of from0.001% by mass to 5% by mass based on the whole nonaqueous electrolyte;and a carbonic acid ester having at least one of an unsaturated bond anda halogen atom in an amount of from 0.001% by mass to 5% by mass basedon the whole nonaqueous electrolyte:

[wherein A and B each represent any of various substituents, providedthat at least one of the substituents represented by A and B isfluorine; and n is a natural number of 3 or larger].
 22. The nonaqueouselectrolyte according to claim 21, wherein the compound represented bygeneral formula (3) is contained in an amount of from 0.001% by volumeto 1% by volume based on the whole nonaqueous electrolyte.
 23. Thenonaqueous electrolyte according to any one of claim 1 to claim 22,which is for use in a nonaqueous-electrolyte secondary battery includinga negative electrode employing an active material comprising acarbonaceous material.
 24. The nonaqueous electrolyte according to anyone of claim 1 to claim 22, which is for use in a nonaqueous-electrolytesecondary battery including a negative electrode employing an activematerial having at least one kind of atom selected from the groupconsisting of aluminum atom, silicon atom, tin atom, lead atom, andtitanium atom.
 25. A nonaqueous-electrolyte secondary battery employingthe nonaqueous electrolyte according to any one of claim 1 to claim 22.26. A nonaqueous-electrolyte secondary battery comprising a negativeelectrode and a positive electrode which are capable ofoccluding/releasing lithium ions and a nonaqueous electrolyte, whereinthe nonaqueous electrolyte is the nonaqueous electrolyte according toany one of claim 1 to claim
 22. 27. The nonaqueous-electrolyte secondarybattery according to claim 26, wherein the negative electrode comprisesa carbonaceous material.
 28. The nonaqueous-electrolyte secondarybattery according to claim 26, wherein the negative electrode comprisesa negative-electrode active material having at least one kind of atomselected from the group consisting of aluminum atom, silicon atom, tinatom, lead atom, and titanium atom.
 29. The nonaqueous-electrolytesecondary battery according to any one of claim 25 to claim 28, whereinthe positive electrode and/or the negative electrode contains at leastone of monofluorophosphate and/or difluorophosphate in the structurethereof.
 30. A nonaqueous electrolyte comprising a lithium salt and anambient-temperature-molten salt, wherein the nonaqueous electrolytecomprises a monofluorophosphate and/or a difluorophosphate.
 31. Thenonaqueous electrolyte according to claim 30, wherein theambient-temperature-molten salt is a tertiary sulfonium salt having astructure represented by the following general formula (6), a quaternaryammonium salt having a structure represented by the following generalformula (7), or a quaternary phosphonium salt having a structurerepresented by the following general formula (8):

[wherein R_(1r), R_(2r), and R_(3r) each independently represent anorganic group having 1-12 carbon atoms, provided that two organic groupsof the R_(1r), R_(2r), and R_(3r) may have been bonded to each other toform a ring structure]

[wherein R_(4r), R_(5r), R_(6r), and R_(7r) each independently representan organic group having 1-12 carbon atoms, provided that two to fourorganic groups of the R_(4r), R_(5r), R_(6r), and R_(7r) may have beenbonded to each other to form a ring structure and that two organicgroups of the R_(4r), R_(5r), R_(6r), and R_(7r) may actually be oneorganic group bonded to the “N⁺” atom through a double bond]

[wherein R_(8r), R_(9r), R_(10r), and R_(11r) each independentlyrepresent an organic group having 1-12 carbon atoms, provided that twoto four organic groups of the R_(8r), R_(9r), R_(10r), and R_(11r) mayhave been bonded to each other to form a ring structure and that twoorganic groups of the R_(8r), R_(9r), R_(10r), and R_(11r) may actuallybe one organic group bonded to the “P⁺” atom through a double bond]. 32.The nonaqueous electrolyte according to claim 30 or claim 31, whereinthe monofluorophosphate and/or difluorophosphate is contained in a totalamount of from 0.001% by mass to 100% by mass based on the wholenonaqueous electrolyte.
 33. The nonaqueous electrolyte according to anyone of claim 30 to claim 32, wherein the ambient-temperature-molten saltis contained in an amount of from 0.01% by mass to 100% by mass based onthe components of the nonaqueous electrolyte other than the lithiumsalt, monofluorophosphate, and difluorophosphate.
 34. Anonaqueous-electrolyte battery comprising a negative electrode and apositive electrode which are capable of occluding and releasing lithiumions and a nonaqueous electrolyte, wherein the nonaqueous electrolyte isthe nonaqueous electrolyte according to anyone of claim 30 to claim 33.35. A nonaqueous electrolyte comprising a nonaqueous solvent and anelectrolyte dissolved therein, wherein the nonaqueous electrolytecomprises: a monofluorophosphate and/or a difluorophosphate; and furtheran iron-group element in an amount of 0.001 ppm or more and less than 1ppm based on the whole nonaqueous electrolyte.
 36. The nonaqueouselectrolyte according to claim 35, wherein the iron-group element iscobalt element and/or nickel element.
 37. The nonaqueous electrolyteaccording to claim 35 or claim 36, wherein the monofluorophosphateand/or difluorophosphate is a difluorophosphate.
 38. The nonaqueouselectrolyte according to any one of claim 35 to claim 37, wherein thetotal content of the monofluorophosphate and/or difluorophosphate isfrom 0.001% by mass to 5% by mass based on the whole nonaqueouselectrolyte.
 39. A nonaqueous-electrolyte secondary battery whichemploys the nonaqueous electrolyte according to any one of claim 35 toclaim
 38. 40. A nonaqueous-electrolyte secondary battery comprising anegative electrode and a positive electrode which are capable ofoccluding/releasing lithium ions and a nonaqueous electrolyte, whereinthe nonaqueous electrolyte is the nonaqueous electrolyte according toany one of claim 35 to claim
 38. 41. The nonaqueous-electrolytesecondary battery according to claim 40, wherein the negative electrodecomprises a carbonaceous material.
 42. The nonaqueous-electrolytesecondary battery according to claim 40, wherein the negative electrodecomprises a negative-electrode active material having at least one kindof atom selected from the group consisting of aluminum atom, siliconatom, tin atom, lead atom, and titanium atom.
 43. Thenonaqueous-electrolyte secondary battery according to anyone of claim 39to claim 42, wherein the positive electrode and/or the negativeelectrode contains at least one of monofluorophosphate and/ordifluorophosphate in the structure thereof.